Research ArticleExploring the Ruthenium-Ligands Bond and Their RelativeProperties at Different Computational Methods
Adebayo A Adeniyi and Peter A Ajibade
Department of Chemistry University of Fort Hare Private Bag Box X1314 Alice 5700 South Africa
Correspondence should be addressed to Peter A Ajibade pajibadeufhacza
Received 21 September 2015 Revised 17 November 2015 Accepted 25 November 2015
Academic Editor Maria F Carvalho
Copyright copy 2016 A A Adeniyi and P A Ajibade This is an open access article distributed under the Creative CommonsAttribution License which permits unrestricted use distribution and reproduction in any medium provided the original work isproperly cited
We report some experimental bond distances and computational models of six ruthenium bonds obtained from DFT to highercomputational methods like MP2 and CCSD The bonds distances geometrical RMSD and the thermodynamic properties of themodels from different computational methods are similar It is observed that optimization of molecules of many light atoms withdifferent functional methods results in significant geometrical variation in the values and order of the computed properties Thevalues of the hyperpolarizabilities HOMO LUMO and isotropic and anisotropic shielding are found to depend greatly on the typeof the functional used and the geometrical variation rather than on the nature of basis set used However all the methods ratedmodelled Ru-S Ru-Cl and Ru-O bonds as having the highest hyperpolarizabilities valuesThe infrared spectra data obtained fromthe different computational methods are significantly different from each other except for MP2 and CCSD which are found to bevery similar
1 Introduction
Ruthenium complexes have received significant considera-tion as conductive optical anticancer and antibiotic applica-tions [1ndash16] Besides great number of ruthenium complexesthere are many of the ruthenium-ligand bonds which arefound relevant to their biological activities The covalentbonding between Ru and N7 (guanine) is considered thepredominant mode of action with DNA for Ru antitumorcompounds [17ndash19] It was also assumed that metals canform chelates with N7 and O6 atoms of guanine [20] Theformation of a hydrolyzed Ru-O bond is very significantfor the activation of ruthenium complexes for biologicalactivities [19 21] The rate of hydrolysis has significant effecton the anticancer activities [22ndash24] Rutheniumhas also beenreported to bind to S of Cys residue of Cathepsin B [25ndash27]Mostly for Ru anticancer activities bonding between Ru andN7 (guanine) is considered to be the predominant mode ofactionwithDNA [17]However it is also possible that bindingto guanine N7 atoms is less important than other types ofinteraction like interaction with phosphate groups hydrogenbonds and so forth [28]
The computational approach is very significant for theoptimization of the complexes and design of novel complexesfor various applications studying their electronic conduc-tive and spectroscopic properties in relation to their stabilityHowever it is computationally expensive to compute theproperties of ruthenium complexes using higher basis setlike aug-cc-pVTZ and high perturbation method like MP2It is therefore highly important to optimize the compu-tational methods which are affordable for the rutheniumcomplexes In this paper we have presented different modelsof ruthenium complexes which are different by the type ofthe ruthenium-ligand (Ru-L) bonds The types of the Ru-L bond of interest to us are Ru-C Ru-N Ru-O Ru-P Ru-S Ru-Cl and Ru-H which are common to many of thesynthesised ruthenium complexes for various applicationsas shown in Table 1 The effects of the functional methodsand the level of basis sets on the Ru-L bond length andtheir relative properties are presented with the intention tofind cheaper and approachable computational methods forruthenium complexes
Hindawi Publishing CorporationJournal of ChemistryVolume 2016 Article ID 3672062 15 pageshttpdxdoiorg10115520163672062
2 Journal of Chemistry
Table 1 The experimental bond distances for Ru-L which are found to be common in different ruthenium complexes
Ru-C Ru-N Ru-O Ru-P Ru-S Ru-Cl Ru-H1827 [44] 1940 to 2137 [45] 200 to 201 [46] 22587 to 23141 [47] 2246 to 2266 [48] 22971 to 23680 [49] 1494 [44]
1845 to 2220 [50] 200 to 2053 [46] 20514 to 2091 [47] 2277 [50] 22777 to 23050 [51] 2327 to 3366 [51] 157 to 159[52]
1865 to 2035 [53] 20190 to 20914 [49] 2058 to 2074 [54] 2279 to 2298 [54] 23436 to 23737 [55] 2359 to 2388 [45]2083 [1] 2024 to 2114 [51] 20656 [51] 22812 to 24188 [52] 23726 to 23885 [53]2109 to 2287 [55] 2025 to 2047 [46] 2066 to 2092 [44] 231 to 2389 [47] 2407 to 2418 [37]2116 to 21777 [43] 2066 to 2196 [56] 2076 to 2109 [49] 23165 to 23679 [57] 2407 to 24511 [46]2199 to 2281 [58] 20703 to 2183 [53] 20783 to 2118 [53] 2336 [46] 2411 to 2434 [54]
20792 [58] 218 to 223 [59] 2363 to 2378 [44] 2431 to 24823 [47]2107 to 2122 [60] 2412 [56] 2434 to 24567 [51]2141 to 2196 [44] 24357 [1]
2 Computational Method
Six models of common ruthenium-ligand bonds which areH5Ru-CH
3 H5Ru-NH
2 H5Ru-OH H
5Ru-Cl H
5Ru-PH
3
and H5Ru-SH
3were built to represent common types of
bonds in ruthenium-ligand complexes and in ruthenium-receptor interactions The models were optimized with DFThybrid functional like PBE [29] and B3LYP [30] and otherhigher computational methods like MP2 and CCSD usingmixed basis sets of SBKJC VDZ [31] for Ru atom and6-31+G(dp) for other atoms Many of the properties arecomputed using DGDZVP for Ru while others were treatedwith 6-31+G(dp) Also for better simulation results themodels were treated with higher perturbation method MP2and at higher basis set aug-cc-pVTZ for all the atomsincluding ruthenium In all the methods all atoms besidesthe Ru atom are treated with 6-31+G(dp) basis set exceptwhen basis sets aug-cc-pVTZ was applied on all atomsTherefore in the methods where different basis set is appliedon Ru atom the method will be reference based on thetype of basis set applied on the Ru atom All the com-putational methods B3LYPSBKJC-VDZ PBESBKJC-VDZMP2SBKJC-VDZ CCSDSBKJC-VDZ B3LYPDGDZVPPBEDGDZVP MP2DGDZVP and CCSDDGDZVP andall other atoms beside Ru atomwere treated with 6-31+G(dp)while in the MP2aug-cc-pVTZ method all the atoms weretreated with the same basis set All the computation was doneusingGaussian 09 [32] and external basis set aug-cc-pVTZ forRu atom EMSL Basis Set Library [33 34] and incorporatedinto the input file in a format that Gaussian 09 programscan readThe first hyperpolarizability tensors were calculatedfrom the Gaussian output using (119887
119894119895119896) = szligtot = (szlig119909
2+ szlig119910
2+
szlig119911
2)12 where szlig
119909= (szlig119909119909119909+ szlig119909119910119910+ szlig119909119911119911) szlig119910= (szlig119910119910119910+ szlig119910119909119909+
szlig119910119911119911) and szlig
119911= (szlig119911119909119909+ szlig119911119910119910+ szlig119911119911119911) [35 36] The atomic
units (au) of szlig in G09 were converted into electrostaticunits (esu) (1 au = 86393 times 10minus33 esu) The IR spectra ofthe molecules were assigned through the method of potentialenergy distribution (PED) contributions as implemented inVEDA package [37] and explained in the literatures [38 39]
3 Results and Discussion
Six models of ruthenium-ligand bonds (Ru-C Ru-N Ru-ORu-Cl Ru-P and Ru-S) are modelled and were optimizedusing the functionals MP2 CCSD PBE and B3LYP Many oftheir properties like their hyperpolarizabilities and isotropicand anisotropic shielding tensors are computed using thefunctionals with different basis sets like SBKJC-VDZRu6-31+G(dp) DGDZVPRu6-31+G(dp) and aug-cc-pVTZ
31 Bonds and the Thermodynamic Properties Dependent onFunctional Methods Different bond distances of ruthenium-ligands (Ru-L) which are reported in the literatures fromtheir crystal structures are shown in Table 1 From thecrystal structures of ruthenium complexes the range of theexperimental bond length for Ru-C is 1827 to 2281 that ofRu-N is 1940 to 2196 that of Ru-O is 200 to 223 that ofRu-Cl is 22971 to 24357 that of Ru-P is 22587 to 2412 thatof Ru-S is 2246 to 23737 and that of Ru-H is 1494 to 159(Table 1)The general features of the experimental Ru-L bondlengths are in the order of Ru-Cl gt Ru-P gt Ru-S gt Ru-O gtRu-N gt Ru-C gt Ru-H The Ru-L bond distances of the sixmodels which are obtained from the optimized geometriesat MP2 CCSD PBE and B3LYP level of theories are shownin Figure 1 The general features of the Ru-L bond lengths ofthe six models using different computational methods showa common order of Ru-P gt Ru-S gt Ru-Cl gt Ru-C gt Ru-O gtRu-N The observed similarity in the bond orders betweenthe experimental and theoretical is that they both rated Ru-Cl Ru-P and Ru-S higher than Ru-O Ru-N and Ru-C Thecomputed range of bond values for Ru-C is 194 to 198 in theorder of MP2 lt PBE lt B3LYP ltCCSD that of Ru-N is 183 to187 in the order of MP2 lt B3LYP lt CCSD lt PBE that of Ru-O is 185 to 187 in the order of MP2 lt CCSD lt B3LYP lt PBEthat of Ru-Cl is 217 to 221 in the order of MP2 lt CCSD ltB3LYP lt PBE that of Ru-P is 239 to 245 in the order ofMP2 lt PBE lt B3LYP lt CCSD and that of Ru-S is 221 to224 in the order of MP2 lt PBE lt B3LYP lt CCSD In bothRu-N and Ru-Cl the functional PBE overestimates the bonds
Journal of Chemistry 3
Ru-C-MP2
Ru-O-MP2
Ru-S-MP2Ru-P-MP2
Ru-Cl-MP2
Ru-N-MP2
Ru-C-CCSD Ru-N-CCSD
Ru-O-CCSD
Ru-S-CCSD
Ru-P-CCSDRu-Cl-CCSD
Ru-C-PBE0
Ru-N-PBE0 Ru-O-PBE0
Ru-S-PBE0Ru-P-PBE0
Ru-Cl-PBE0
Ru-C-B3LYP Ru-N-B3LYP
Ru-O-B3LYP
Ru-S-B3LYP
Ru-P-B3LYPRu-Cl-B3LYP
1964 1980 1949 1951 1839 1878
1834 2116 1864 1861 1850 1874
2210 2208 2171 2480 2437 2448
2397 2419 2228 2237 2216 2223
Figure 1The bond distances of the six models of Ru-L bonds obtained from the optimized geometries at MP2 CCSD PBE and B3LYP usingSBKJC VDZ basis set
Table 2 The bond distances and thermodynamic properties using MP2ECP method and the differences using other methods (energies inKJMol)
Methodbonds Distance Energy Zero energy Thermal energy Enthalpy Gibbs-free CV KJMol-K 119878 KJMol-KRu-C-MP2-ECP 19485 minus35376119864 + 05 minus35457119864 + 05 minus35455119864 + 05 minus35455119864 + 05 minus35464119864 + 05 00782 02901
Ru-N-MP2-ECP 18342 minus35376119864 + 05 minus35457119864 + 05 minus35455119864 + 05 minus35455119864 + 05 minus35464119864 + 05 00782 02901
Ru-O-MP2-ECP 18501 minus39584119864 + 05 minus39681119864 + 05 minus39679119864 + 05 minus39679119864 + 05 minus39688119864 + 05 00769 02940
Ru-Cl-MP2-ECP 21711 minus44927119864 + 05 minus45022119864 + 05 minus45021119864 + 05 minus45021119864 + 05 minus45029119864 + 05 00736 02927
Ru-P-MP2-ECP 23969 minus11493119864 + 06 minus11499119864 + 06 minus11499119864 + 06 minus11499119864 + 06 minus11500119864 + 06 00973 03293
Ru-S-MP2-ECP 22157 minus12964119864 + 06 minus12973119864 + 06 minus12972119864 + 06 minus12972119864 + 06 minus12973119864 + 06 00855 03188
Difference of the other methods fromMP2SBKJC VDZRu-C-PBE-ECP 00024 minus29890119864 + 03 minus19950119864 + 03 minus19946119864 + 03 minus19946119864 + 03 minus19955119864 + 03 00017 00032
Ru-N-PBE-ECP 00120 minus29890119864 + 03 minus19950119864 + 03 minus19946119864 + 03 minus19946119864 + 03 minus19955119864 + 03 00017 00032
Ru-O-PBE-ECP 00243 minus31318119864 + 03 minus19966119864 + 03 minus19970119864 + 03 minus19970119864 + 03 minus19959119864 + 03 minus00011 minus00037
Ru-Cl-PBE-ECP 03088 minus32116119864 + 03 minus21228119864 + 03 minus21223119864 + 03 minus21223119864 + 03 minus21231119864 + 03 00021 00027
Ru-P-PBE-ECP 00219 minus35356119864 + 03 minus27378119864 + 03 minus27373119864 + 03 minus27373119864 + 03 minus27386119864 + 03 00009 00043
Ru-S-PBE-ECP 00074 minus37839119864 + 03 minus28207119864 + 03 minus28208119864 + 03 minus28208119864 + 03 minus28202119864 + 03 00007 minus00019
Ru-C-B3LYP-ECP 00159 minus31831119864 + 03 minus21836119864 + 03 minus21828119864 + 03 minus21828119864 + 03 minus21844119864 + 03 00039 00055
Ru-N-B3LYP-ECP 00047 minus45407119864 + 04 minus44429119864 + 04 minus44429119864 + 04 minus44429119864 + 04 minus44429119864 + 04 minus00012 00010
Ru-O-B3LYP-ECP 00144 minus33288119864 + 03 minus21890119864 + 03 minus21893119864 + 03 minus21893119864 + 03 minus21884119864 + 03 00000 minus00028
Ru-Cl-B3LYP-ECP 00392 minus34479119864 + 03 minus23536119864 + 03 minus23531119864 + 03 minus23531119864 + 03 minus23540119864 + 03 00022 00031
Ru-P-B3LYP-ECP 00398 minus40797119864 + 03 minus32774119864 + 03 minus32764119864 + 03 minus32764119864 + 03 minus32788119864 + 03 00031 00081
Ru-S-B3LYP-ECP 00125 minus43126119864 + 03 minus33423119864 + 03 minus33431119864 + 03 minus33431119864 + 03 minus33414119864 + 03 minus00029 minus00057
Ru-C-CCSD-ECP 00316 minus21515119864 + 01 minus71138119864 + 01 minus69570119864 + 01 minus69570119864 + 01 minus72697119864 + 01 00075 00105
Ru-N-CCSD-ECP 00436 minus42095119864 + 04 minus42295119864 + 04 minus42294119864 + 04 minus42294119864 + 04 minus42295119864 + 04 00024 00047
Ru-O-CCSD-ECP 00109 minus16767119864 + 01 minus54986119864 + 01 minus54600119864 + 01 minus54600119864 + 01 minus54878119864 + 01 00037 00009
Ru-Cl-CCSD-ECP 00368 minus24604119864 + 01 minus65007119864 + 01 minus64330119864 + 01 minus64330119864 + 01 minus65559119864 + 01 00037 00041
Ru-P-CCSD-ECP 00512 minus14740119864 + 00 minus12560119864 + 02 minus12351119864 + 02 minus12351119864 + 02 minus12915119864 + 02 00066 00189
Ru-S-CCSD-ECP 00211 minus37429119864 + 01 minus98966119864 + 01 minus99562119864 + 01 minus99562119864 + 01 minus98230119864 + 01 minus00017 minus00045
above other functional methods Ru-C bond values of ourmodel are within the common experimental bond values forRu-C while the values obtained for other modelled bondsare little below the common experimental values If the bondvalues obtained using theMP2 are compared to the analyticalvalues the differences in the values of other computational
methods from MP2 are calculated using simple expression119883other minus119883MP2 and are presented in Table 2The differences inbond values obtained using PBE compared to the analyticalvalues fromMP2 are smaller inmagnitude compared to othermethods (Table 2) but the order of the bond distances in themodel was not perfectly reproduced as in B3LYP and CCSD
4 Journal of Chemistry
HH
H
H
H
H
HHH
H
H
Cl
S
OC
RuRu
Ru
RuRuRu
P
N
Figure 2 The superposition of different model of Ru-L bonds obtained using MP2 (green) CCSD (blue) PBE (yellow) and B3LYP (cyan)to determine the RMSD of the whole geometries after the optimization of their respective geometries
Table 3 The correlation of the values of energy and thermody-namics properties at MP2SBKJC VDZ with other computationalmethods
MP2-ECP PBE B3LYP CCSDRu-L-dist 100 100 100Energy 100 100 100Zero energy 100 100 100Thermal energy 100 100 100Enthalpy 100 100 100Gibbs-free 100 100 100CV 099 097 095Entropy 098 095 092
(Table 3) All the thermodynamic properties were computedat 298150 Kelvin and pressure 1 Atm The magnitude ofthe differences in thermodynamic properties (Table 2) showsthat CCSD and PBE give closer values to MP2 than B3LYPAlso considering the reproducibility of the order of bonddistances obtained from MP2 in the other methods all thecomputational methods produced a perfect order for thethermodynamic energies except PBE which gave a relativelybetter order for the CV and the entropy (Table 3) Thisis an indication that PBE performs better for geometricaloptimization and computation of thermodynamic propertieswhich agree well with the literatures that reported PBEcorrelation in combination with SBKJC VDZ ECP basis setas a good method for the optimization of metal complexes[40 41]The computed types of energies using othermethodsof computation are higher in negative values thanMP2 whiletheir bond distance CV and S are higher in positive valuesConsidering the RMSD of all the atoms in each of the modelsas shown in Table 4 and Figure 2 the optimized geometriesobtained for the models Ru-C Ru-O and Ru-S at variouscomputational methods are very similar to lower RMSDcompared to what was obtained for the models Ru-N Ru-Cl and Ru-P Also the RMSD of the optimized geometriesobtained from the functional PBE are lower than those
Table 4 The RMSD of the optimized geometries obtained fromother methods of computation from that obtained from MP2 usingSBKJC VDZ ECP basis set
B3LYP CCSD PBERu-C 0963 1347 0637Ru-N 1030 1032 1035Ru-O 0056 0072 0065Ru-Cl 1302 1030 1268Ru-P 1203 1221 1190Ru-S 0265 0266 0252
obtained from B3LYP and CCSD which further supportsPBE as a good method for the optimization of rutheniumcomplexes
32 Energy HOMO LUMO Shielding Tensors and J-Coupling The values of the energy HOMO LUMO andisotropic and anisotropic shielding computed atMP2aug-cc-pVTZ and the variations obtainedwhen computedwith othermethods are presented in Table 5 The shielding tensors werecomputed using Gauge-Independent Atomic Orbital (GIAO)method The values of the energy and the variation obtainedat different functional and basis sets show that variation in theenergy values using different functional is lower comparedto variation in the energy values using different basis setsThis is an indication that the energy values depend moreon the type of basis sets rather than on the type of thefunctional However the variation in the values of HOMOLUMO and isotropic and anisotropic shielding at differentfunctional methods shows that they depend more on thetype of the functional and the geometrical change rather thanon the type of the basis sets The difference in the valuesof HOMO LUMO and isotropic and anisotropic shieldingwithin MP2 methods at different basis set is lower comparedto changing the functional to PBE and B3LYP Also B3LYPseems to perform better than PBE as the differences obtainedat B3LYP are far lower compared to PBE Also consideringthe reproducibility of the order of these properties at different
Journal of Chemistry 5
Table 5The energy shielding tensors and 119869-coupling values usingMP2acc method and the differences using other computational methods(the energy values in Hartree)
Energy HOMO LUMO Ru-Iso Ru-Aniso X-Iso X-AnisoRu-C-MP2-acc minus440352 minus092 minus042 minus742180 1069111 minus14988 52269
Ru-N-MP2-acc minus441877 minus090 minus046 minus1176015 946597 minus82579 178860
Ru-O-MP2-acc minus443924 minus068 minus018 minus918858 846675 minus16694 119428
Ru-Cl-MP2-acc minus482319 minus062 minus020 minus1122411 1052228 29822 238476
Ru-P-MP2-acc minus470544 minus087 minus037 minus1359081 1488590 44861 4141
Ru-S-MP2-acc minus476385 minus061 minus016 minus313338 582699 minus80439 237577
000Ru-C-MP2-dv minus7849 000 000 26183 minus38901 1148 659
Ru-N-MP2-dv minus7926 000 minus001 71088 minus70110 3343 minus1344
Ru-O-MP2-dv minus7914 000 000 minus44694 minus39512 minus13768 24327
Ru-Cl-MP2-dv minus7924 000 000 minus37254 114475 minus19716 35479
Ru-P-MP2-dv minus7957 000 000 minus177917 246557 2518 minus037
Ru-S-MP2-dv minus7719 002 minus002 minus611650 135558 minus20580 35851
Ru-C-MP2-ECP 426878 000 minus001 596528 minus920085 1311 193
Ru-N-MP2- ECP 426800 000 000 960319 minus813149 7435 minus7455
Ru-O-MP2- ECP 426812 000 000 740324 minus715956 minus8299 15674
Ru-Cl-MP2- ECP 426802 000 000 914427 minus867435 minus16484 41130
Ru-P-MP2- ECP 426770 000 minus001 1093680 minus1218157 3260 minus1317
Ru-S-MP2- ECP 427007 003 minus003 149743 minus496580 13797 minus14494
Ru-C-PBE-dv minus8075 020 minus022 minus5106 minus767006 34929 minus46155
Ru-N-PBE-dv minus8156 018 minus020 629261 minus496409 52642 minus92641
Ru-O-PBE-dv minus8147 022 minus018 13816439 15984243 minus383942 413974
Ru-Cl-PBE-dv minus8176 015 minus018 10321955 13287550 minus491003 4370795
Ru-P-PBE-dv minus8201 021 minus021 16547451 37324221 374088 1446238
Ru-S-PBE-dv minus7973 018 minus019 10654331 10347455 minus659068 1230739
Ru-C-PBE-ECP 426764 021 minus021 663760 minus1027535 7597 minus17075
Ru-N-PBE-ECP 426681 018 minus020 1071404 minus884998 53035 minus93320
Ru-O-PBE-ECP 426690 022 minus018 minus3381033 38277943 minus3091812 35041247
Ru-Cl-PBE-ECP 426660 015 minus018 minus757542 2579402 27160896
Ru-P-PBE-ECP 426635 021 minus021 19109900 96261433
Ru-S-PBE-ECP 426863 018 minus019 9522596 32119344 11565209 35835334
Ru-C-B3LYP-dv minus8128 016 minus018 81227 minus588737 4860 minus12006
Ru-N-B3LYP-dv minus8211 013 minus017 431991 minus275591 45112 minus75540
Ru-O-B3LYP-dv minus8203 017 minus016 273324 minus381398 minus23391 6813
Ru-Cl-B3LYP-dv minus8246 012 minus016 254850 minus284675 minus265807 309548
Ru-P-B3LYP-dv minus8270 016 minus019 472561 minus646413 minus5451 9137
Ru-S-B3LYP-dv minus8041 014 minus017 minus225901 minus250444 30708 minus72243
Ru-C-B3LYP-ECP 426757 016 minus018 624966 minus1003953 4904 minus12301
Ru-N-B3LYP-ECP 426673 013 minus017 1040250 minus853188 45960 minus77145
Ru-O-B3LYP-ECP 426681 017 minus016 802053 minus780523 minus19773 minus244
Ru-Cl-B3LYP-ECP 426638 012 minus016 977624 minus948089 minus236464 264500
Ru-P-B3LYP-ECP 426614 016 minus018 1207902 minus1376028 minus4806 7968
Ru-S-B3LYP-ECP 426843 014 minus017 212424 minus536594 33276 minus74643
MP2-acc stands for MP2aug-cc-pVTZ MP2-dv stands for MP2DGDZVP MP2-ECP stands for MP2SBKJC VDZ PBE-dv stands for PBEDGDZVP PBE-ECP stands for PBESBKJC VDZ B3LYP-dv stands for B3LYPDGDZVP and B3LYP-ECP stands for B3LYPSBKJC VDZ
6 Journal of Chemistry
Table 6 Correlation of othermethods of computation with theMP2acc in computing energy HOMO LUMO and isotropic and anisotropicshielding
MP2DGDZVP MP2SBKJC VDZ PBEDGDZVP PBESBKJC VDZ B3LYPDGDZVP B3LYPSBKJC VDZEnergy 100 100 100 100 100 100
HOMO 100 100 099 099 099 099
LUMO 100 100 100 099 100 100
Ru-Iso 074 083 minus009 minus011 091 094
Ru-Aniso 095 097 051 050 084 082
X-Iso 098 098 067 minus051 minus016 minus012
X-Aniso 099 098 minus035 033 071 073
Table 7 119869-coupling of the Ru-L bonds at different level of computational methods
PBEDGDZVP PBESBKJC VDZ B3LYPDGDZVP B3LYPSBKJC VDZRu-C minus185119864 + 001 114119864 + 000 minus268119864 + 000 136119864 + 000
Ru-N minus146119864 + 001 753119864 minus 001 656119864 + 001 607119864 + 000
Ru-O 245119864 + 001 minus980119864 minus 001 249119864 + 001 minus117119864 + 000
Ru-Cl 472119864 + 001 563119864 + 000 476119864 + 001 590119864 + 000
Ru-P minus651119864 + 001 minus314119864 minus 001 minus714119864 + 001 minus500119864 minus 001
Ru-S minus752119864 minus 001 106119864 + 000 469119864 minus 001 135119864 + 000
Table 8 Correlation of 119869-coupling within the methods
PBEDGDZVP PBESBKJC VDZ B3LYPDGDZVP B3LYPSBKJC VDZPBE-dv 100 058 074 037PBE-ECP 058 100 042 073B3LYP-dv 074 042 100 072B3LYP-ECP 037 073 072 100
computational methods (Table 6) only the energy order isperfectly reproduced by all the methods There is a veryhigh similarity in the order of HOMO and LUMO especiallyLUMO computed using B3LYP In addition B3LYP is foundto also perform better in reproducing the shielding tensors ofRu and other atoms compared to PBE except for the orderof the isotropic shielding of other atoms besides Ru atomThe correlation obtained fromB3LYP in computing shieldingtensors further supports its reported better performance forthese properties [42]
In computation of the 119869-coupling we are only limited toB3LYP and PBE since these properties are not permitted inGaussian package at MP2 and CCSD level of theories Con-sidering the magnitude of 119869-coupling at B3LYPDGDZVP itfollows the order Ru-P gt Ru-N gt Ru-Cl gt Ru-S gt Ru-O gtRu-C (Table 7) The order is well reproduced in B3LYP withECP basis set but is poor in PBE and is even the worst whenPBE is combined with ECP basis set (Table 8) The simplereason for the variations is in support of the literature reportdemonstrating that the 119869-coupling is sensitive to bondinginteractions [43]
33 Hyperpolarizability Properties The values of the com-puted hyperpolarizabilities of the six models using differentfunctionals and basis sets are shown in Table 9 The values ofthe hyperpolarizabilities of themodels usingMP2 functionalsat different basis sets are in the order of Ru-S gt Ru-O gt Ru-Cl gt Ru-N gt Ru-P gt Ru-C which suggest the level of theirpossible modelling for NLO application The order obtained
from CCSD is Ru-O gt Ru-Cl gt Ru-S gt Ru-P gt Ru-N gt Ru-C the PBE methods give the order Ru-Cl gt Ru-C lt Ru-S gtRu-O gt Ru-P gt Ru-N and B3LYP gives the order Ru-Cl gtRu-O gt Ru-S gt Ru-P gt Ru-N gt Ru-C The MP2 rated Ru-S as the best model for NLO application while CCSD ratedmodel Ru-O as the best Also a different model Ru-Cl isindicated to have the highest hyperpolarizabilities using thefunctionals PBE and B3LYP irrespective of the basis set usedThe correlations of the hyperpolarizabilities values among themodels are shown in Table 10 The correlation table showsthat the order of the hyperpolarizabilities of the models isperfectly reproducible using the same MP2 at different basissets and also within CCSD at different basis sets Also B3LYPperforms better in reproducing its order at different basisset compared to PBE This clearly shows that the order ofthe hyperpolarizabilities depends greatly on the geometricalconfiguration and the type of the functional used rather thanon the type of the basis sets The only observed similarity inthe order of the hyperpolarizabilities computed with differentmethods is that all the methods rated the models Ru-S Ru-Cl and Ru-O among the best three except for PBE whichexcluded Ru-O from its best three
34 The IR Vibrations The IR vibrations of the modelsat different computational methods are shown in Figure 3The vibrations which are of significant interest to us aretheir Ru-ligand bonds of Ru-C Ru-N Ru-O Ru-Cl Ru-Pand Ru-S which are shown in Table 11 Also most of theprominent vibrations are assigned as shown in Table 12 In
Journal of Chemistry 7
Table9Th
efirsth
yperpo
lariz
ability(szlig)inesu(1times10minus30)v
aluesa
tdifferentcom
putatio
nalm
etho
ds
MP2
aug-cc-pV
TZMP2
DGDZV
PMP2
SBK
JCVDZ
CCSD
DGDZV
PCC
SDSBK
JCVDZ
PBEDGDZV
PPB
ESB
KJCVDZ
B3LY
PDGDZV
PB3
LYPSB
KJCVDZ
Ru-C
153
179
171
108
098
244
028
055
055
Ru-N
569
224
380
105
109
077
063
076
062
Ru-O
3505
1791
1860
822
548
178
160
220
205
Ru-C
l1173
1440
1325
558
547
284
289
325
313
Ru-P
177
180
213
124
151
152
147
135
137
Ru-S
28214
33591
11477
8295
315
214
182
207
165
8 Journal of Chemistry
Table10Th
ecorrelationwith
inthed
ifferentm
etho
dsused
incompu
tingthefi
rsth
yperpo
lariz
abilitie
s
MP2
aug-cc-pV
TZMP2
DGDZV
PMP2
SBK
JCVDZ
CCSD
DGDZV
PCC
SDSBK
JCVDZ
PBEDGDZV
PPB
ESB
KJCVDZ
B3LY
PDGDZV
PB3
LYPSB
KJCVDZ
MP2
-acc
100
100
100
004
014
019
030
024
010
MP2
-dv
100
100
100
minus001
010
020
029
022
009
MP2
-ecp
100
100
100
minus005
006
019
027
019
006
CCSD
-dv
004
minus001
minus005
100
095
031
062
075
075
CCSD
-ECP
014
010
006
095
100
045
081
092
091
PBE-dv
019
020
019
031
045
100
042
051
053
PBE-EC
P030
029
027
062
081
042
100
097
095
B3LY
P-dv
024
022
019
075
092
051
097
100
099
B3LY
P-EC
P010
009
006
075
091
053
095
099
100
Journal of Chemistry 9
200 300 400 500 600 700200 300 400 500 600 700
200 300 400 500 600 700200 300 400 500 600 700
200 300 400 500 600 700200 300 400 500 600 700
Ru-C-MP2Ru-C-CCSD
Ru-C-PBE0Ru-C-B3LYP
Ru-N-MP2Ru-N-CCSD
Ru-N-PBE0Ru-N-B3LYP
Ru-O-MP2Ru-O-CCSD
Ru-O-PBE0Ru-O-B3LYP
Ru-Cl-MP2Ru-Cl-CCSD
Ru-Cl-PBE0Ru-Cl-B3LYP
Ru-P-MP2Ru-P-CCSD
Ru-P-PBE0Ru-P-B3LYP
Ru-S-MP2Ru-S-CCSD
Ru-S-PBE0Ru-S-B3LYP
Figure 3 The IR vibrations of the six models computed using MP2 (black) CCSD (red) PBE (green) and B3LYP (blue)
10 Journal of Chemistry
Table11Th
eIRvibrations
oftheR
u-Lbo
ndsa
tdifferentcom
putatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
6077
72349120573(H
RuH)120592(Ru-C)
5872
73346120592(Ru-C)
68224
195
120592(Ru-C)
63297
226
120573(H
RuH)120592(Ru-C)
50222
238
120591(H
RuCH
)120592(Ru-C)
53062
71120573(H
RuH)120592(Ru-C)
Ru-N
71899
977
120592(Ru-N)120592(Ru-H)
62352
1636120592(Ru-N)
66265
2879120573(H
RuH)120592(Ru-N)
71495
1013
120592(Ru-N)
48235
101120592(Ru-N)
49539
738
120592(Ru-N)
65608
137
120573(H
RuH)120592(Ru-N)
Ru-O
7178
11371
120592(Ru-O)
63412
1586120592(Ru-O)
70574
75120592(Ru-O)
68889
2395
120592(Ru-O)
Ru-C
l43529
2195
120592(Ru-Cl)
5913
3644
120592(Ru-Cl)
65732
376
120592(Ru-Cl)
32331
1022
120592(Ru-Cl)
4478
43433
120592(Ru-Cl)
Ru-P
28203
171
120592(Ru-P)
2393
9395
120592(Ru-P)
44535
232
120592(Ru-P)
2793
71025
o(Ru
HPH
)120592(Ru-P)
23442
711
o(Ru
HPH
)120592(Ru-P)
Ru-S
4119
4401
120592(Ru-S)
32619
424
120592(Ru-S)
3574
92496
o(Ru
HSH
)120592(Ru-S)
40866
311
120592(Ru-S)
37311
597
o(Ru
HSH
)120592(Ru-S)
38596
1999
120592(Ru-S)
120592isstr
etching120573isbend
ing120591istorsionalandoisou
t-of-p
lane
torsional
Journal of Chemistry 11
Table12Th
eassignm
ento
fthe
prom
inentIRvibrations
ofthem
odels
atdifferent
compu
tatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
346783
9624120573(H
RuH)120592(Ru-H)
386628
124120573(H
RuH)120573(H
RuH)
120592(C
H)120592(Ru-H)
381759
1510
1120573(H
RuH)120573(H
RuH)
120591(H
RuHC)
30511
103120592(C
H)o(Ru
HCH
)120592(C
H)
313241
8772
120592(C
H)120592(C
H)
344585
6003
120592(Ru-H)
326534
582120573(H
CH)120592(C
H)120592(Ru-H)
3044
61
5191120592(C
H)o(Ru
HCH
)120592(Ru-H)
306501
5614120573(H
RuH)120573(H
RuH)
o(Ru
HCH
)323718
7402120573(H
CH)120573(H
RuH)120592(C
H)
310576
7913
120573(H
RuH)120592(Ru-H)
29104116677
120592(C
H)120592(C
H)
299873
14381
120592(C
H)120592(C
H)
310607
10481120573(H
RuC)
120591(H
CRuH
)o(Ru
HCH
)230969
6851120573(H
RuH)120591(H
RuHC)
120592(Ru-H)
247128
4498120573(H
RuH)o(Ru
HCH
)120592(Ru-H)
240085
1095
1120592(C
H)
231944
1014
7120573(H
RuC)
o(RuH
CH)
207553
969120573(H
RuH)120573(H
RuH)
120592(Ru-H)120592(Ru-H)
232314
1296
8120592(C
H)
Ru-N
38020714205120573(H
RuH)120573(H
RuH)
120573(H
RuH)
401043
1231120573(H
RuH)120591(H
RuHN)
120592(N
H)
403478
11428120591(H
RuNH)o(Ru
HNH)
120592(N
H)
353289
10673120573(H
RuH)120573(H
RuH)
339019
20019
120592(N
H)120592(N
H)
347897
18119120573(H
RuH)120573(H
RuH)
120591(H
RuHN)120592(Ru-H)
347497
1866120573(H
RuH)120573(H
RuH)
120592(Ru-H)
331504
19282
120592(N
H)120592(N
H)
32687139839
120592(N
H)120592(N
H)
336728
2897
5120592(Ru-H)
332695
1499
5120573(H
RuH)o(Ru
HNH)
318372
37524
120592(N
H)120592(N
H)
293151
4214120592(Ru-H)120592(Ru-H)120592(N
H)
120592(N
H)
327085
3514120573(H
RuH)120591(H
RuHN)
120592(Ru-H)
2746
17455
o(Ru
HNH)120592(Ru-H)
120592(Ru-H)
238961
4007120573(H
RuH)120592(Ru-H)
207916
6108
120592(Ru-H)
199979
4338
120573(H
NH)
210524
6443
o(Ru
HNH)120592(N
H)
120592(Ru-H)
203734
6557
120592(Ru-H)
Ru-O
372613
2694
9120592(O
H)
380749
28041
o(Ru
HOH)120592(Ru-H)
389061
1005
o(Ru
HOH)120573(H
RuH)
3608772399
3120592(O
H)
275932
1407120573(H
RuH)o(Ru
HOH)
o(Ru
HOH)120592(Ru-H)
31079
1921120573(H
RuO)120573(H
RuH)
o(Ru
HOH)
370979
51891120573(H
RuO)120573(H
RuO)
327956
2992120573(H
RuH)120573(H
RuH)
18598
2333
120592(Ru-H)120592(Ru-H)
179443
2374120573(H
RuH)o(Ru
HOH)
120592(Ru-H)
291506
5502
o(Ru
HOH)120592(Ru-H)
120592(Ru-H)
220079
1599120573(H
RuH)o(Ru
HOH)
120592(Ru-H)120592(Ru-H)
1346
08
2894120592(Ru-H)120592(Ru-H)
125632
2895120592(Ru-H)120573(H
ORu
)260461
4569120592(O
H)120573(H
ORu
)203014
1588
120592(Ru-H)
112741
9479120573(H
RuH)120592(Ru-H)
120592(Ru-H)
109235
7374
120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
205106
3383120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
147934
29120592(Ru-H)120592(Ru-H)
Ru-C
l185546
2458
120592(Ru-H)
308667
1411120573(H
RuH)o(Ru
HClH)
120592(Ru-H)
30365123653
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
22088
2242
120592(Ru-H)
131751
3288
120592(Ru-H)
179947
2511
o(Ru
HClH)120592(Ru-H)
120592(Ru-H)
261179
3015
120592(Ru-H)120573(H
RuH)
210816
1124
120592(Ru-H)
114581
9421
120592(Ru-H)
121159
3269120573(H
RuH)120573(H
RuH)
120573(H
RuCl)
20399
3006120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
203112
1687
120592(Ru-H)
84759
3157
120592(Ru-H)
110861
7222
o(Ru
HClH)o(Ru
HClH)
120592(Ru-H)120573(H
RuCl)
131224
3565
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
147293
3151
120592(Ru-H)
79488
381
120573(H
RuH)
7687
2483120573(H
RuH)120592(Ru-H)
120592(Ru-H)120592(Ru-H)
109164
1501120592(Ru-H)120573(H
RuH)
11346
9195
3120573(H
RuH)
12 Journal of Chemistry
Table12C
ontin
ued
B3LY
PCC
SDMP2
PBE
Ru-P
384575
1547
120573(H
RuH)
40856716207120573(H
RuH)120591(H
RuPH
)o(Ru
HPH
)410148
11361120573(H
RuH)120573(H
RuH)
3509879645120573(H
RuH)120592(Ru-H)
296363
1457120573(H
RuH)120592(Ru-H)
328227
1508120573(H
RuH)120573(H
RuH)
120591(H
PRuH
)264975
4273
120573(H
RuP)120592(Ru-H)
246259
4871
120592(PH)120592(PH)
253628
4006
120592(PH)120592(PH)
261721
3138
120592(Ru-H)
262336
4752
120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
24307
5689
120592(PH)120592(PH)
250603
4624
120592(PH)120592(PH)
259379
3579
120573(H
RuP)
256933
4865120573(H
RuP)120573
(HRu
H)
238468
1306120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
245899
7096
120592(PH)120592(PH)
255419
4427120573(H
RuH)120591(H
PRuH
)120591(H
PRuH
)228633
8692
120573(H
RuH)120592(PH)
237354
92120592(PH)
Ru-S
265041
1308
120592(SH)
290793
378120573(H
RuH)120591(H
SRuH
)120592(Ru-H)120573(H
RuS)
417199
15487
o(Ru
HSH
)o(Ru
HSH
)120573(H
RuH)
34606
2384120573(H
RuH)120573(H
RuH)
120573(H
RuH)o(Ru
HSH
)
26342
1916
120573(H
RuH)120592(Ru-H)
188073
1685120573(H
RuH)120573(H
RuH)
120592(Ru-H)
28041
199265120573(H
RuS)120573
(HRu
H)
120573(H
RuH)120592(Ru-H)
258225
1254
120592(SH)
1913
1699
120592(Ru-H)
114853
2967120591(H
SRuH
)120592(SH)
120592(Ru-H)
2385442392374
120573(H
RuS)
21675
2604
120592(Ru-H)
121642
3386120592(Ru-H)120592(Ru-H)
109859
10132120573(H
RuH)120591(H
SRuH
)o(Ru
HSH
)120592(Ru-H)
225761
44894
120592(Ru-H)120573(H
RuH)
132047
3699120592(Ru-H)120592(Ru-H)
11086
11006120573(H
RuH)120592(Ru-H)
82534
331120591(H
SRuH
)120592(Ru-H)
120592(Ru-H)
210643
5205
120592(Ru-H)
8835
5098
o(Ru
HSH
)o(Ru
HSH
)120592(Ru-H)120592(Ru-H)
Journal of Chemistry 13
all the methods Ru-C Ru-N and Ru-O vibrations are withinthe range of 500 to 720 which is far higher than the rangeof vibrations of Ru-Cl Ru-P and Ru-S which are foundwithin the range of 224 to 658 Generally the order of Ru-L vibrations can be assumed as Ru-N gt Ru-O gt Ru-C gtRu-Cl gt Ru-S gt Ru-P (Table 11) The wavenumbers of thevibrations computed from the different methods appear to besignificantly different from each other in values and positions(Figure 3) The features of the IR spectra using MP2 andCCSD are very similar in the models Some vibration around291506 in model Ru-O 303651 in Ru-Cl and 238544 inRu-S are very prominent in MP2 methods compared to inany other methods or even absent in other methods Forinstance the bending of the angle of HRuS which is found tobe prominent in MP2 method is completely absent in othermethods (see Figure 3 and Table 12) The MP2 and CCSDshow strong vibrations within the range of 3800 to 4100 inmany of the models which are obviously absent in manyof the PBE and B3LYP methods Using the PED methodas implemented in VEDA package most of these vibrationsat high frequencies are a result of the torsional and out-of-plane vibration of H-Ru-X-H where X represents the typeof the model as shown in Table 12 In addition most of thebending vibrations which are determined by PBE and B3LYPfrom 2800 to 3800 in the models are also determined byMP2 and CCSD though some cases are at lower wavenumbercompared to PBE and B3LYP (Table 12) In the models Ru-Oand Ru-Cl PBE and B3LYP give priority to the OH and RuHvibrations respectively whileMP2 andCCSD give priority tothe torsional stretching and angle bending of their atoms
4 Conclusions
Six models of Ru-L bonds Ru-C Ru-N Ru-O Ru-Cl Ru-P and Ru-S are built to represent common rutheniumcomplexes and possible ruthenium-receptor interactionsThe reproducibility of their geometrical electronic spec-troscopic and conductive properties was investigated usingMP2 CCSD PBE and B3LYP functionals with differentcombination of basis sets Generally we observed that thereproducibility of most of the properties is much easier usingdifferent basis sets compared to using different functionalmethods as a result of significant geometrical changes whichis possible especially if there are many light atoms likehydrogen atoms as in themodelsThe order of the energy andthe thermodynamic properties are found to be reproducibleusing different functionalmethods and basis sets butHOMOLUMO 119869-coupling hyperpolarizabilities and isotropic andanisotropic shielding are found to depend more on the typeof the functional used rather than on the type of the basis setThe only significant similarity observed among the methodsapplied in computing hyperpolarizabilities is that they allrated models Ru-S Ru-Cl and Ru-O among their best threeThe optimized geometries and the thermodynamic proper-ties obtained from the functional PBE are found to be verysimilar to MP2 and perform better than B3LYP and CCSDwhich further give insight into many literaturesrsquo preferencefor PBE in optimizing metal complexes In computation ofthe isotropic and anisotropic shielding tensors B3LYP gives
values similar to MP2 and performs better than PBE The IRvibrations and assignment clearly show that the vibrationsobtained from the MP2 and CCSD methods are very similarand give preference to the torsional and bending vibrationsof the molecules over their stretching The order of the IRvibrations of the ruthenium-ligand bonds can be assumed asRu-N gt Ru-O gt Ru-C gt Ru-Cl gt Ru-S gt Ru-P
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
The authors gracefully acknowledged the financial support ofGovan Mbeki Research and Development Centre Universityof Fort Hare South Africa The CHPC in Republic ofSouth Africa is gracefully acknowledged for providing thecomputing facilities and some of the software used for thecomputation
References
[1] B Dutta R Scopelliti and K Severin ldquoSynthesis structure andreactivity of the methoxy-bridged dimer [CpandRu(120583-OMe)]
2
(Cpand = 1205785-1-methoxy-24-di-tert-butyl-3-neopentylcyclopenta-dienyl)rdquo Organometallics vol 27 no 3 pp 423ndash429 2008
[2] M A Furrer F Schmitt M Wiederkehr L Juillerat-Jeanneretand B Therrien ldquoCellular delivery of pyrenyl-arene rutheniumcomplexes by a water-soluble arene ruthenium metalla-cagerdquoDalton Transactions vol 41 no 24 pp 7201ndash7211 2012
[3] Q ZhouW Lei YChen et al ldquoRuthenium(II)-arene complexeswith strong fluorescence insight into the underlying mecha-nismrdquoChemistrymdashA European Journal vol 18 no 28 pp 8617ndash8621 2012
[4] L Bıro E Farkas and P Buglyo ldquoHydrolytic behaviour andchloride ion binding capability of [Ru(1205786 minus119901minus cym)(H
2O)3]2+
a solution equilibrium studyrdquoDalton Transactions vol 41 no 1pp 285ndash291 2012
[5] Y Boutadla D L Davies R C Jones and K Singh ldquoThescope of ambiphilic acetate-assisted cyclometallation with half-sandwich complexes of iridium rhodium and rutheniumrdquoChemistrymdashA European Journal vol 17 no 12 pp 3438ndash34482011
[6] Y F Han H Li Y Fei Y J Lin W Z Zhang and GX Jin ldquoSynthesis and structural characterization of binuclearhalf-sandwich iridium rhodium and ruthenium complexescontaining 441015840-dipyridyldisulfide (4DPDS) ligandsrdquo DaltonTransactions vol 39 no 30 pp 7119ndash7124 2010
[7] B Dutta B F Curchod P Campomanes et al ldquoReactions ofalkynes with [RuCl(cyclopentadienyl)] complexes the impor-tant first stepsrdquo ChemistrymdashA European Journal vol 16 no 28pp 8400ndash8409 2010
[8] M Jimenez-Tenorio M C Puerta P Valerga S MonchoG Ujaque and A Lledos ldquoProton-transfer reactions to half-sandwich ruthenium trihydride complexes bearing hemilabilePN ligands experimental and density functional theory stud-iesrdquo Inorganic Chemistry vol 49 no 13 pp 6035ndash6057 2010
14 Journal of Chemistry
[9] B Dutta C Scolaro R Scopelliti P J Dyson and K Sev-erin ldquoImportance of the 120587-ligand remarkable effect of thecyclopentadienyl ring on the cytotoxicity of ruthenium PTAcompoundsrdquoOrganometallics vol 27 no 7 pp 1355ndash1357 2008
[10] T Bugarcic A Habtemariam J Stepankova et al ldquoThe con-trasting chemistry and cancer cell cytotoxicity of bipyridineand bipyridinediol ruthenium(II) arene complexesrdquo InorganicChemistry vol 47 no 24 pp 11470ndash11486 2008
[11] M Castellano-Castillo H Kostrhunova V Marini et al ldquoBind-ing ofmismatch repair proteinMutS tomispairedDNA adductsof intercalating ruthenium(II) arene complexesrdquo Journal ofBiological Inorganic Chemistry vol 13 no 6 pp 993ndash999 2008
[12] S J Dougan A Habtemariam S E McHale S Parsons andP J Sadler ldquoCatalytic organometallic anticancer complexesrdquoProceedings of the National Academy of Sciences of the UnitedStates of America vol 105 no 33 pp 11628ndash11633 2008
[13] S J Dougan M Melchart A Habtemariam S Parsons and PJ Sadler ldquoPhenylazo-pyridine and phenylazo-pyrazole chloridoruthenium(II) arene complexes arene loss aquation and can-cer cell cytotoxicityrdquo Inorganic Chemistry vol 45 no 26 pp10882ndash10894 2006
[14] V Ritleng P Bertani M Pfeffer C Sirlin and J HirschingerldquoOptically active ortho-metalated half-sandwich rutheniumcomplexes solid-state NMR as a convenient tool to analyzemixtures of diastereomersrdquo Inorganic Chemistry vol 40 no 20pp 5117ndash5122 2001
[15] Y Sunada Y Hayashi H Kawaguchi and K TatsumildquoAlkynethiolato and alkyneselenolato rutheniumhalf-sandwichcomplexes Synthesis structures and reactions with (1205785ndashC5H5)2Zrrdquo Inorganic Chemistry vol 40 no 27 pp 7072ndash70782001
[16] K Yamanari R Ito S Yamamoto et al ldquoCyclic tetramerscomposed of rhodium(III) iridium(III) or ruthenium(II) half-sandwich and6-purinethionesrdquo Inorganic Chemistry vol 41 no25 pp 6824ndash6830 2002
[17] F Caruso M Rossi A Benson et al ldquoRuthenium-arenecomplexes of curcumin X-ray and density functional the-ory structure synthesis and spectroscopic characterizationin vitro antitumor activity and DNA docking studies of (p-cymene)Ru(curcuminato)chlorordquo Journal of Medicinal Chem-istry vol 55 no 3 pp 1072ndash1081 2012
[18] C Gossens I Tavernelli and U Rothlisberger ldquoBinding oforganometallic ruthenium(II) anticancer compounds to nucle-obases a computational studyrdquo Journal of Physical Chemistry Avol 113 no 43 pp 11888ndash11897 2009
[19] A M Pizarro A Habtemariam and P J Sadler ldquoActiva-tion mechanisms for organometallic anticancer complexesrdquoin Medicinal Organometallic Chemistry vol 32 of Topics inOrganometallic Chemistry pp 21ndash56 Springer Berlin Ger-many 2010
[20] I Turel and J Kljun ldquoInteractions of metal ions with DNAits constituents and derivatives which may be relevant foranticancer researchrdquoCurrent Topics inMedicinal Chemistry vol11 no 21 pp 2661ndash2687 2011
[21] G Gasser I Ott and N Metzler-Nolte ldquoOrganometallic anti-cancer compoundsrdquo Journal of Medicinal Chemistry vol 54 no1 pp 3ndash25 2011
[22] K J Kilpin S Crot T Riedel J A Kitchen and P JDyson ldquoRuthenium(II) and osmium(II) 123-triazolylideneorganometallics a preliminary investigation into the biologicalactivity of rsquoclickrsquo carbene complexesrdquo Dalton Transactions vol43 no 3 pp 1443ndash1448 2014
[23] A F A Peacock S Parsons and P J Sadler ldquoTuning thehydrolytic aqueous chemistry of osmium arene complexeswith NO-chelating ligands to achieve cancer cell cytotoxicityrdquoJournal of the American Chemical Society vol 129 no 11 pp3348ndash3357 2007
[24] A F A Peacock M Melchart R J Deeth A Habtemariam SParsons and P J Sadler ldquoOsmium(II) and ruthenium(II) arenemaltolato complexes rapid hydrolysis and nucleobase bindingrdquoChemistrymdashA European Journal vol 13 no 9 pp 2601ndash26132007
[25] F Pelletier V Comte A Massard et al ldquoDevelopment ofbimetallic titanoceneminusrutheniumminusarene complexes as anti-cancer agents relationships between structural and biologicalpropertiesrdquo Journal of Medicinal Chemistry vol 53 no 19 pp6923ndash6933 2010
[26] K J Kilpin and P J Dyson ldquoEnzyme inhibition by metalcomplexes concepts strategies and applicationsrdquo ChemicalScience vol 4 no 4 pp 1410ndash1419 2013
[27] G Gasser andNMetzler-Nolte ldquoThe potential of organometal-lic complexes in medicinal chemistryrdquo Current Opinion inChemical Biology vol 16 no 1-2 pp 84ndash91 2012
[28] I Turel J Kljun F Perdih et al ldquoFirst ruthenium organometal-lic complex of antibacterial agent ofloxacin Crystal structureand interactions with DNArdquo Inorganic Chemistry vol 49 no23 pp 10750ndash10752 2010
[29] C Adamo and V Barone ldquoToward reliable density functionalmethods without adjustable parameters the PBE0 modelrdquoJournal of Chemical Physics vol 110 no 13 pp 6158ndash6170 1999
[30] A D Becke ldquoDensity-functional thermochemistry IIIThe roleof exact exchangerdquoThe Journal of Chemical Physics vol 98 no7 article 5648 1993
[31] W J Stevens M Krauss H Basch and P G Jasien ldquoRelativisticcompact effective potentials and efficient shared-exponentbasis sets for the third- fourth- and fifth-row atomsrdquoCanadianJournal of Chemistry vol 70 no 2 pp 612ndash630 1992
[32] M J Frisch GW Trucks H B Schlegel et alOfficial Gaussian09 Literature Citation Gaussian Wallingford UK 2009
[33] D J Feller ldquoThe role of databases in support of computationalchemistry calculationsrdquo Journal of Computational Chemistryvol 17 no 13 pp 1571ndash1586 1996
[34] K L Schuchardt B T Didier T Elsethagen et al ldquoBasis setexchange a community database for computational sciencesrdquoJournal of Chemical Information andModeling vol 47 no 3 pp1045ndash1052 2007
[35] Y Liu C-G Liu S-L Sun G-C Yang and Y-Q QiuldquoRedox-switching second-order nonlinear optical responses ofNandNandN ruthenium complexesrdquo Computational and TheoreticalChemistry vol 979 pp 112ndash118 2012
[36] P S Liyanage R M de Silva and K M N de Silva ldquoNonlinearoptical (NLO) properties of novel organometallic complexeshigh accuracy density functional theory (DFT) calculationsrdquoJournal of Molecular Structure THEOCHEM vol 639 pp 195ndash201 2003
[37] MH Jamroz ldquoVibrational EnergyDistributionAnalysis VEDA4 ProgramrdquoWarsaw Poland 2004ndash2010 httpwwwsmmgpl
[38] M H Jamroz J C Dobrowolski and R Brzozowski ldquoVibra-tional modes of 26- 27- and 23-diisopropylnaphthalene ADFT studyrdquo Journal of Molecular Structure vol 787 no 1ndash3 pp172ndash183 2006
[39] M H Jamroz ldquoVibrational Energy Distribution Analysis(VEDA) scopes and limitationsrdquo Spectrochimica Acta AMolec-ular and Biomolecular Spectroscopy vol 114 pp 220ndash230 2013
Journal of Chemistry 15
[40] R Marchal P Carbonniere D Begue and C Pouchan ldquoStruc-tural and vibrational determination of small galliumndasharsenideclusters fromCCSD(T) andDFT calculationsrdquoChemical PhysicsLetters vol 453 no 1ndash3 pp 49ndash54 2008
[41] R Marchal P Carbonniere and C Pouchan ldquoStructural andvibrational properties prediction of Sn
119899Te119899clusters (n = 2ndash
8) using the GSAM approachrdquo Computational and TheoreticalChemistry vol 990 pp 100ndash105 2012
[42] T Helgaker M Jaszunski and M Pecul ldquoThe quantum-chemical calculation of NMR indirect spin-spin coupling con-stantsrdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 53 no 4 pp 249ndash268 2008
[43] F A Perras andD L Bryce ldquoTheoretical study of homonuclear Jcoupling between quadrupolar spins single-crystal DOR andJ-resolved NMRrdquo Journal of Magnetic Resonance vol 242 pp23ndash32 2014
[44] I D Burns A F Hill A J P White D J Williams and J DE T Wilton-Ely ldquoPolyazolyl chelate chemistry 61 bidentatecoordination of HB(pz)
3(pz = Pyrazol-1-yl) to ruthenium and
osmium crystal structure of [RuH(CO)(PPh3)2k2-HB(pz)
3]rdquo
Organometallics vol 17 no 8 pp 1552ndash1557 1998[45] M Al-Noaimi and M A AlDamen ldquoRuthenium complexes
incorporating azoimine and 120572-diamine based ligands synthe-sis crystal structure electrochemistry and DFT calculationrdquoInorganica Chimica Acta vol 387 pp 45ndash51 2012
[46] K Nakajima Y Ando H Mano and M Kojima ldquoPhotosub-stitution reactivity crystal structures and electrochemistry ofruthenium(II) (III) complexes containing tetradentate (O
2N2
S2N2 and P
2N2) Schiff base ligandsrdquo Inorganica Chimica Acta
vol 274 no 2 pp 184ndash191 1998[47] Z-L Lu K Eichele I Warad et al ldquoSupported organometal-
lic complexes XXXVIII [1] Bis(methoxyethyldimethlphos-phine)ruthenium(II) complexes as transfer hydrogenation cat-alystsrdquo Zeitschrift fur Anorganische und Allgemeine Chemie vol629 no 7-8 pp 1308ndash1315 2003
[48] R Gaur and L Mishra ldquoSynthesis and characterization ofRu(II)ndashDMSOndashClndashchalcone complexes DNA binding nucle-ase and topoisomerase II inhibitory activityrdquo Inorganic Chem-istry vol 51 no 5 pp 3059ndash3070 2012
[49] B Cebrian-Losantos E Reisner C R Kowol et al ldquoSynthesisand reactivity of the aquation product of the antitumor complextrans-[Ru IIICI
4(indazole)
2] minusrdquo Inorganic Chemistry vol 47 no
14 pp 6513ndash6523 2008[50] B T Rasley M Rapta and R J Kulawiec ldquoDiastereoselectivity
in enolate coordination in a new class of chiral rutheniumenolate complexesrdquo Organometallics vol 15 no 13 pp 2852ndash2854 1996
[51] S David R S Perkins F R Fronczek S Kasiri S S MandalandR S Srivastava ldquoSynthesis characterization and anticanceractivity of ruthenium-pyrazole complexesrdquo Journal of InorganicBiochemistry vol 111 pp 33ndash39 2012
[52] B Dutta E Solari S Gauthier R Scopelliti and K SeverinldquoRuthenium half-sandwich complexes with sterically demand-ing cyclopentadienyl ligandsrdquo Organometallics vol 26 no 19pp 4791ndash4799 2007
[53] G Turkoglu S Tampier F Strinitz F W Heinemann E Hub-ner and N Burzlaff ldquoRuthenium carbonyl complexes bearingbis(pyrazol-1-yl)carboxylato ligandsrdquo Organometallics vol 31no 6 pp 2166ndash2174 2012
[54] A K Renfrew A D Phillips E Tapavicza R ScopellitiU Rothlisberger and P J Dyson ldquoTuning the efficacy of
ruthenium(II)-arene (RAPTA) antitumor compounds with flu-orinated arene ligandsrdquo Organometallics vol 28 no 17 pp5061ndash5071 2009
[55] P M Jeffries R E Ellenwood and G S Girolami ldquoAnionicruthenium(II) alkyls with ancillary diene and dienyl ligandssynthesis and structures of [(12057821205782-C
7H8)RuMe
4]2minus and [(12057831205782-
C8H11)RuMe
3]2minusrdquo Inorganica Chimica Acta vol 361 no 1 pp
3165ndash3170 2008[56] B R James D Dolphin T W Leung F W B Einstein
and A C Willis ldquoPreparation and characterization of someruthenium(III) porphyrins including the crystal structure ofbromo(octaethylporphinato)(triphenylphosphine)ruthenium(III)rdquoCanadian Journal of Chemistry vol 62 no 7 pp 1238ndash12451984
[57] M Plois R Wolf W Hujo and S Grimme ldquoTowards reagentsfor bimetallic activation reactions polyhydride complexes withRu2H3 Ru2ZnH6 and Cu
2Ru2H6coresrdquo European Journal of
Inorganic Chemistry vol 2013 no 17 pp 3039ndash3048 2013[58] L Hintermann L Xiao A Labonne and U Englert
ldquo[CpRu(1205786-naphthalene)]PF6as precursor in complex synthesis
and catalysis with the cyclopentadienyl-ruthenium(II) cationrdquoOrganometallics vol 28 no 19 pp 5739ndash5748 2009
[59] I W Wyman K N Robertson T S Cameron J C SwartsandM A S Aquino ldquoSynthesis structure and electrochemistryof (ferrocene-2-propenoato-OO1015840)bis[12-bis(diphenylphosphi-no)ethane-PP1015840]ruthenium(II) hexafluorophosphaterdquo Inorgan-ica Chimica Acta vol 359 no 9 pp 3092ndash3096 2006
[60] C A Vock C Scolaro A D Phillips R Scopelliti G Sava andP J Dyson ldquoSynthesis characterization and in vitro evaluationof novel ruthenium(II) 1205786-arene imidazole complexesrdquo Journalof Medicinal Chemistry vol 49 no 18 pp 5552ndash5561 2006
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
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CatalystsJournal of
2 Journal of Chemistry
Table 1 The experimental bond distances for Ru-L which are found to be common in different ruthenium complexes
Ru-C Ru-N Ru-O Ru-P Ru-S Ru-Cl Ru-H1827 [44] 1940 to 2137 [45] 200 to 201 [46] 22587 to 23141 [47] 2246 to 2266 [48] 22971 to 23680 [49] 1494 [44]
1845 to 2220 [50] 200 to 2053 [46] 20514 to 2091 [47] 2277 [50] 22777 to 23050 [51] 2327 to 3366 [51] 157 to 159[52]
1865 to 2035 [53] 20190 to 20914 [49] 2058 to 2074 [54] 2279 to 2298 [54] 23436 to 23737 [55] 2359 to 2388 [45]2083 [1] 2024 to 2114 [51] 20656 [51] 22812 to 24188 [52] 23726 to 23885 [53]2109 to 2287 [55] 2025 to 2047 [46] 2066 to 2092 [44] 231 to 2389 [47] 2407 to 2418 [37]2116 to 21777 [43] 2066 to 2196 [56] 2076 to 2109 [49] 23165 to 23679 [57] 2407 to 24511 [46]2199 to 2281 [58] 20703 to 2183 [53] 20783 to 2118 [53] 2336 [46] 2411 to 2434 [54]
20792 [58] 218 to 223 [59] 2363 to 2378 [44] 2431 to 24823 [47]2107 to 2122 [60] 2412 [56] 2434 to 24567 [51]2141 to 2196 [44] 24357 [1]
2 Computational Method
Six models of common ruthenium-ligand bonds which areH5Ru-CH
3 H5Ru-NH
2 H5Ru-OH H
5Ru-Cl H
5Ru-PH
3
and H5Ru-SH
3were built to represent common types of
bonds in ruthenium-ligand complexes and in ruthenium-receptor interactions The models were optimized with DFThybrid functional like PBE [29] and B3LYP [30] and otherhigher computational methods like MP2 and CCSD usingmixed basis sets of SBKJC VDZ [31] for Ru atom and6-31+G(dp) for other atoms Many of the properties arecomputed using DGDZVP for Ru while others were treatedwith 6-31+G(dp) Also for better simulation results themodels were treated with higher perturbation method MP2and at higher basis set aug-cc-pVTZ for all the atomsincluding ruthenium In all the methods all atoms besidesthe Ru atom are treated with 6-31+G(dp) basis set exceptwhen basis sets aug-cc-pVTZ was applied on all atomsTherefore in the methods where different basis set is appliedon Ru atom the method will be reference based on thetype of basis set applied on the Ru atom All the com-putational methods B3LYPSBKJC-VDZ PBESBKJC-VDZMP2SBKJC-VDZ CCSDSBKJC-VDZ B3LYPDGDZVPPBEDGDZVP MP2DGDZVP and CCSDDGDZVP andall other atoms beside Ru atomwere treated with 6-31+G(dp)while in the MP2aug-cc-pVTZ method all the atoms weretreated with the same basis set All the computation was doneusingGaussian 09 [32] and external basis set aug-cc-pVTZ forRu atom EMSL Basis Set Library [33 34] and incorporatedinto the input file in a format that Gaussian 09 programscan readThe first hyperpolarizability tensors were calculatedfrom the Gaussian output using (119887
119894119895119896) = szligtot = (szlig119909
2+ szlig119910
2+
szlig119911
2)12 where szlig
119909= (szlig119909119909119909+ szlig119909119910119910+ szlig119909119911119911) szlig119910= (szlig119910119910119910+ szlig119910119909119909+
szlig119910119911119911) and szlig
119911= (szlig119911119909119909+ szlig119911119910119910+ szlig119911119911119911) [35 36] The atomic
units (au) of szlig in G09 were converted into electrostaticunits (esu) (1 au = 86393 times 10minus33 esu) The IR spectra ofthe molecules were assigned through the method of potentialenergy distribution (PED) contributions as implemented inVEDA package [37] and explained in the literatures [38 39]
3 Results and Discussion
Six models of ruthenium-ligand bonds (Ru-C Ru-N Ru-ORu-Cl Ru-P and Ru-S) are modelled and were optimizedusing the functionals MP2 CCSD PBE and B3LYP Many oftheir properties like their hyperpolarizabilities and isotropicand anisotropic shielding tensors are computed using thefunctionals with different basis sets like SBKJC-VDZRu6-31+G(dp) DGDZVPRu6-31+G(dp) and aug-cc-pVTZ
31 Bonds and the Thermodynamic Properties Dependent onFunctional Methods Different bond distances of ruthenium-ligands (Ru-L) which are reported in the literatures fromtheir crystal structures are shown in Table 1 From thecrystal structures of ruthenium complexes the range of theexperimental bond length for Ru-C is 1827 to 2281 that ofRu-N is 1940 to 2196 that of Ru-O is 200 to 223 that ofRu-Cl is 22971 to 24357 that of Ru-P is 22587 to 2412 thatof Ru-S is 2246 to 23737 and that of Ru-H is 1494 to 159(Table 1)The general features of the experimental Ru-L bondlengths are in the order of Ru-Cl gt Ru-P gt Ru-S gt Ru-O gtRu-N gt Ru-C gt Ru-H The Ru-L bond distances of the sixmodels which are obtained from the optimized geometriesat MP2 CCSD PBE and B3LYP level of theories are shownin Figure 1 The general features of the Ru-L bond lengths ofthe six models using different computational methods showa common order of Ru-P gt Ru-S gt Ru-Cl gt Ru-C gt Ru-O gtRu-N The observed similarity in the bond orders betweenthe experimental and theoretical is that they both rated Ru-Cl Ru-P and Ru-S higher than Ru-O Ru-N and Ru-C Thecomputed range of bond values for Ru-C is 194 to 198 in theorder of MP2 lt PBE lt B3LYP ltCCSD that of Ru-N is 183 to187 in the order of MP2 lt B3LYP lt CCSD lt PBE that of Ru-O is 185 to 187 in the order of MP2 lt CCSD lt B3LYP lt PBEthat of Ru-Cl is 217 to 221 in the order of MP2 lt CCSD ltB3LYP lt PBE that of Ru-P is 239 to 245 in the order ofMP2 lt PBE lt B3LYP lt CCSD and that of Ru-S is 221 to224 in the order of MP2 lt PBE lt B3LYP lt CCSD In bothRu-N and Ru-Cl the functional PBE overestimates the bonds
Journal of Chemistry 3
Ru-C-MP2
Ru-O-MP2
Ru-S-MP2Ru-P-MP2
Ru-Cl-MP2
Ru-N-MP2
Ru-C-CCSD Ru-N-CCSD
Ru-O-CCSD
Ru-S-CCSD
Ru-P-CCSDRu-Cl-CCSD
Ru-C-PBE0
Ru-N-PBE0 Ru-O-PBE0
Ru-S-PBE0Ru-P-PBE0
Ru-Cl-PBE0
Ru-C-B3LYP Ru-N-B3LYP
Ru-O-B3LYP
Ru-S-B3LYP
Ru-P-B3LYPRu-Cl-B3LYP
1964 1980 1949 1951 1839 1878
1834 2116 1864 1861 1850 1874
2210 2208 2171 2480 2437 2448
2397 2419 2228 2237 2216 2223
Figure 1The bond distances of the six models of Ru-L bonds obtained from the optimized geometries at MP2 CCSD PBE and B3LYP usingSBKJC VDZ basis set
Table 2 The bond distances and thermodynamic properties using MP2ECP method and the differences using other methods (energies inKJMol)
Methodbonds Distance Energy Zero energy Thermal energy Enthalpy Gibbs-free CV KJMol-K 119878 KJMol-KRu-C-MP2-ECP 19485 minus35376119864 + 05 minus35457119864 + 05 minus35455119864 + 05 minus35455119864 + 05 minus35464119864 + 05 00782 02901
Ru-N-MP2-ECP 18342 minus35376119864 + 05 minus35457119864 + 05 minus35455119864 + 05 minus35455119864 + 05 minus35464119864 + 05 00782 02901
Ru-O-MP2-ECP 18501 minus39584119864 + 05 minus39681119864 + 05 minus39679119864 + 05 minus39679119864 + 05 minus39688119864 + 05 00769 02940
Ru-Cl-MP2-ECP 21711 minus44927119864 + 05 minus45022119864 + 05 minus45021119864 + 05 minus45021119864 + 05 minus45029119864 + 05 00736 02927
Ru-P-MP2-ECP 23969 minus11493119864 + 06 minus11499119864 + 06 minus11499119864 + 06 minus11499119864 + 06 minus11500119864 + 06 00973 03293
Ru-S-MP2-ECP 22157 minus12964119864 + 06 minus12973119864 + 06 minus12972119864 + 06 minus12972119864 + 06 minus12973119864 + 06 00855 03188
Difference of the other methods fromMP2SBKJC VDZRu-C-PBE-ECP 00024 minus29890119864 + 03 minus19950119864 + 03 minus19946119864 + 03 minus19946119864 + 03 minus19955119864 + 03 00017 00032
Ru-N-PBE-ECP 00120 minus29890119864 + 03 minus19950119864 + 03 minus19946119864 + 03 minus19946119864 + 03 minus19955119864 + 03 00017 00032
Ru-O-PBE-ECP 00243 minus31318119864 + 03 minus19966119864 + 03 minus19970119864 + 03 minus19970119864 + 03 minus19959119864 + 03 minus00011 minus00037
Ru-Cl-PBE-ECP 03088 minus32116119864 + 03 minus21228119864 + 03 minus21223119864 + 03 minus21223119864 + 03 minus21231119864 + 03 00021 00027
Ru-P-PBE-ECP 00219 minus35356119864 + 03 minus27378119864 + 03 minus27373119864 + 03 minus27373119864 + 03 minus27386119864 + 03 00009 00043
Ru-S-PBE-ECP 00074 minus37839119864 + 03 minus28207119864 + 03 minus28208119864 + 03 minus28208119864 + 03 minus28202119864 + 03 00007 minus00019
Ru-C-B3LYP-ECP 00159 minus31831119864 + 03 minus21836119864 + 03 minus21828119864 + 03 minus21828119864 + 03 minus21844119864 + 03 00039 00055
Ru-N-B3LYP-ECP 00047 minus45407119864 + 04 minus44429119864 + 04 minus44429119864 + 04 minus44429119864 + 04 minus44429119864 + 04 minus00012 00010
Ru-O-B3LYP-ECP 00144 minus33288119864 + 03 minus21890119864 + 03 minus21893119864 + 03 minus21893119864 + 03 minus21884119864 + 03 00000 minus00028
Ru-Cl-B3LYP-ECP 00392 minus34479119864 + 03 minus23536119864 + 03 minus23531119864 + 03 minus23531119864 + 03 minus23540119864 + 03 00022 00031
Ru-P-B3LYP-ECP 00398 minus40797119864 + 03 minus32774119864 + 03 minus32764119864 + 03 minus32764119864 + 03 minus32788119864 + 03 00031 00081
Ru-S-B3LYP-ECP 00125 minus43126119864 + 03 minus33423119864 + 03 minus33431119864 + 03 minus33431119864 + 03 minus33414119864 + 03 minus00029 minus00057
Ru-C-CCSD-ECP 00316 minus21515119864 + 01 minus71138119864 + 01 minus69570119864 + 01 minus69570119864 + 01 minus72697119864 + 01 00075 00105
Ru-N-CCSD-ECP 00436 minus42095119864 + 04 minus42295119864 + 04 minus42294119864 + 04 minus42294119864 + 04 minus42295119864 + 04 00024 00047
Ru-O-CCSD-ECP 00109 minus16767119864 + 01 minus54986119864 + 01 minus54600119864 + 01 minus54600119864 + 01 minus54878119864 + 01 00037 00009
Ru-Cl-CCSD-ECP 00368 minus24604119864 + 01 minus65007119864 + 01 minus64330119864 + 01 minus64330119864 + 01 minus65559119864 + 01 00037 00041
Ru-P-CCSD-ECP 00512 minus14740119864 + 00 minus12560119864 + 02 minus12351119864 + 02 minus12351119864 + 02 minus12915119864 + 02 00066 00189
Ru-S-CCSD-ECP 00211 minus37429119864 + 01 minus98966119864 + 01 minus99562119864 + 01 minus99562119864 + 01 minus98230119864 + 01 minus00017 minus00045
above other functional methods Ru-C bond values of ourmodel are within the common experimental bond values forRu-C while the values obtained for other modelled bondsare little below the common experimental values If the bondvalues obtained using theMP2 are compared to the analyticalvalues the differences in the values of other computational
methods from MP2 are calculated using simple expression119883other minus119883MP2 and are presented in Table 2The differences inbond values obtained using PBE compared to the analyticalvalues fromMP2 are smaller inmagnitude compared to othermethods (Table 2) but the order of the bond distances in themodel was not perfectly reproduced as in B3LYP and CCSD
4 Journal of Chemistry
HH
H
H
H
H
HHH
H
H
Cl
S
OC
RuRu
Ru
RuRuRu
P
N
Figure 2 The superposition of different model of Ru-L bonds obtained using MP2 (green) CCSD (blue) PBE (yellow) and B3LYP (cyan)to determine the RMSD of the whole geometries after the optimization of their respective geometries
Table 3 The correlation of the values of energy and thermody-namics properties at MP2SBKJC VDZ with other computationalmethods
MP2-ECP PBE B3LYP CCSDRu-L-dist 100 100 100Energy 100 100 100Zero energy 100 100 100Thermal energy 100 100 100Enthalpy 100 100 100Gibbs-free 100 100 100CV 099 097 095Entropy 098 095 092
(Table 3) All the thermodynamic properties were computedat 298150 Kelvin and pressure 1 Atm The magnitude ofthe differences in thermodynamic properties (Table 2) showsthat CCSD and PBE give closer values to MP2 than B3LYPAlso considering the reproducibility of the order of bonddistances obtained from MP2 in the other methods all thecomputational methods produced a perfect order for thethermodynamic energies except PBE which gave a relativelybetter order for the CV and the entropy (Table 3) Thisis an indication that PBE performs better for geometricaloptimization and computation of thermodynamic propertieswhich agree well with the literatures that reported PBEcorrelation in combination with SBKJC VDZ ECP basis setas a good method for the optimization of metal complexes[40 41]The computed types of energies using othermethodsof computation are higher in negative values thanMP2 whiletheir bond distance CV and S are higher in positive valuesConsidering the RMSD of all the atoms in each of the modelsas shown in Table 4 and Figure 2 the optimized geometriesobtained for the models Ru-C Ru-O and Ru-S at variouscomputational methods are very similar to lower RMSDcompared to what was obtained for the models Ru-N Ru-Cl and Ru-P Also the RMSD of the optimized geometriesobtained from the functional PBE are lower than those
Table 4 The RMSD of the optimized geometries obtained fromother methods of computation from that obtained from MP2 usingSBKJC VDZ ECP basis set
B3LYP CCSD PBERu-C 0963 1347 0637Ru-N 1030 1032 1035Ru-O 0056 0072 0065Ru-Cl 1302 1030 1268Ru-P 1203 1221 1190Ru-S 0265 0266 0252
obtained from B3LYP and CCSD which further supportsPBE as a good method for the optimization of rutheniumcomplexes
32 Energy HOMO LUMO Shielding Tensors and J-Coupling The values of the energy HOMO LUMO andisotropic and anisotropic shielding computed atMP2aug-cc-pVTZ and the variations obtainedwhen computedwith othermethods are presented in Table 5 The shielding tensors werecomputed using Gauge-Independent Atomic Orbital (GIAO)method The values of the energy and the variation obtainedat different functional and basis sets show that variation in theenergy values using different functional is lower comparedto variation in the energy values using different basis setsThis is an indication that the energy values depend moreon the type of basis sets rather than on the type of thefunctional However the variation in the values of HOMOLUMO and isotropic and anisotropic shielding at differentfunctional methods shows that they depend more on thetype of the functional and the geometrical change rather thanon the type of the basis sets The difference in the valuesof HOMO LUMO and isotropic and anisotropic shieldingwithin MP2 methods at different basis set is lower comparedto changing the functional to PBE and B3LYP Also B3LYPseems to perform better than PBE as the differences obtainedat B3LYP are far lower compared to PBE Also consideringthe reproducibility of the order of these properties at different
Journal of Chemistry 5
Table 5The energy shielding tensors and 119869-coupling values usingMP2acc method and the differences using other computational methods(the energy values in Hartree)
Energy HOMO LUMO Ru-Iso Ru-Aniso X-Iso X-AnisoRu-C-MP2-acc minus440352 minus092 minus042 minus742180 1069111 minus14988 52269
Ru-N-MP2-acc minus441877 minus090 minus046 minus1176015 946597 minus82579 178860
Ru-O-MP2-acc minus443924 minus068 minus018 minus918858 846675 minus16694 119428
Ru-Cl-MP2-acc minus482319 minus062 minus020 minus1122411 1052228 29822 238476
Ru-P-MP2-acc minus470544 minus087 minus037 minus1359081 1488590 44861 4141
Ru-S-MP2-acc minus476385 minus061 minus016 minus313338 582699 minus80439 237577
000Ru-C-MP2-dv minus7849 000 000 26183 minus38901 1148 659
Ru-N-MP2-dv minus7926 000 minus001 71088 minus70110 3343 minus1344
Ru-O-MP2-dv minus7914 000 000 minus44694 minus39512 minus13768 24327
Ru-Cl-MP2-dv minus7924 000 000 minus37254 114475 minus19716 35479
Ru-P-MP2-dv minus7957 000 000 minus177917 246557 2518 minus037
Ru-S-MP2-dv minus7719 002 minus002 minus611650 135558 minus20580 35851
Ru-C-MP2-ECP 426878 000 minus001 596528 minus920085 1311 193
Ru-N-MP2- ECP 426800 000 000 960319 minus813149 7435 minus7455
Ru-O-MP2- ECP 426812 000 000 740324 minus715956 minus8299 15674
Ru-Cl-MP2- ECP 426802 000 000 914427 minus867435 minus16484 41130
Ru-P-MP2- ECP 426770 000 minus001 1093680 minus1218157 3260 minus1317
Ru-S-MP2- ECP 427007 003 minus003 149743 minus496580 13797 minus14494
Ru-C-PBE-dv minus8075 020 minus022 minus5106 minus767006 34929 minus46155
Ru-N-PBE-dv minus8156 018 minus020 629261 minus496409 52642 minus92641
Ru-O-PBE-dv minus8147 022 minus018 13816439 15984243 minus383942 413974
Ru-Cl-PBE-dv minus8176 015 minus018 10321955 13287550 minus491003 4370795
Ru-P-PBE-dv minus8201 021 minus021 16547451 37324221 374088 1446238
Ru-S-PBE-dv minus7973 018 minus019 10654331 10347455 minus659068 1230739
Ru-C-PBE-ECP 426764 021 minus021 663760 minus1027535 7597 minus17075
Ru-N-PBE-ECP 426681 018 minus020 1071404 minus884998 53035 minus93320
Ru-O-PBE-ECP 426690 022 minus018 minus3381033 38277943 minus3091812 35041247
Ru-Cl-PBE-ECP 426660 015 minus018 minus757542 2579402 27160896
Ru-P-PBE-ECP 426635 021 minus021 19109900 96261433
Ru-S-PBE-ECP 426863 018 minus019 9522596 32119344 11565209 35835334
Ru-C-B3LYP-dv minus8128 016 minus018 81227 minus588737 4860 minus12006
Ru-N-B3LYP-dv minus8211 013 minus017 431991 minus275591 45112 minus75540
Ru-O-B3LYP-dv minus8203 017 minus016 273324 minus381398 minus23391 6813
Ru-Cl-B3LYP-dv minus8246 012 minus016 254850 minus284675 minus265807 309548
Ru-P-B3LYP-dv minus8270 016 minus019 472561 minus646413 minus5451 9137
Ru-S-B3LYP-dv minus8041 014 minus017 minus225901 minus250444 30708 minus72243
Ru-C-B3LYP-ECP 426757 016 minus018 624966 minus1003953 4904 minus12301
Ru-N-B3LYP-ECP 426673 013 minus017 1040250 minus853188 45960 minus77145
Ru-O-B3LYP-ECP 426681 017 minus016 802053 minus780523 minus19773 minus244
Ru-Cl-B3LYP-ECP 426638 012 minus016 977624 minus948089 minus236464 264500
Ru-P-B3LYP-ECP 426614 016 minus018 1207902 minus1376028 minus4806 7968
Ru-S-B3LYP-ECP 426843 014 minus017 212424 minus536594 33276 minus74643
MP2-acc stands for MP2aug-cc-pVTZ MP2-dv stands for MP2DGDZVP MP2-ECP stands for MP2SBKJC VDZ PBE-dv stands for PBEDGDZVP PBE-ECP stands for PBESBKJC VDZ B3LYP-dv stands for B3LYPDGDZVP and B3LYP-ECP stands for B3LYPSBKJC VDZ
6 Journal of Chemistry
Table 6 Correlation of othermethods of computation with theMP2acc in computing energy HOMO LUMO and isotropic and anisotropicshielding
MP2DGDZVP MP2SBKJC VDZ PBEDGDZVP PBESBKJC VDZ B3LYPDGDZVP B3LYPSBKJC VDZEnergy 100 100 100 100 100 100
HOMO 100 100 099 099 099 099
LUMO 100 100 100 099 100 100
Ru-Iso 074 083 minus009 minus011 091 094
Ru-Aniso 095 097 051 050 084 082
X-Iso 098 098 067 minus051 minus016 minus012
X-Aniso 099 098 minus035 033 071 073
Table 7 119869-coupling of the Ru-L bonds at different level of computational methods
PBEDGDZVP PBESBKJC VDZ B3LYPDGDZVP B3LYPSBKJC VDZRu-C minus185119864 + 001 114119864 + 000 minus268119864 + 000 136119864 + 000
Ru-N minus146119864 + 001 753119864 minus 001 656119864 + 001 607119864 + 000
Ru-O 245119864 + 001 minus980119864 minus 001 249119864 + 001 minus117119864 + 000
Ru-Cl 472119864 + 001 563119864 + 000 476119864 + 001 590119864 + 000
Ru-P minus651119864 + 001 minus314119864 minus 001 minus714119864 + 001 minus500119864 minus 001
Ru-S minus752119864 minus 001 106119864 + 000 469119864 minus 001 135119864 + 000
Table 8 Correlation of 119869-coupling within the methods
PBEDGDZVP PBESBKJC VDZ B3LYPDGDZVP B3LYPSBKJC VDZPBE-dv 100 058 074 037PBE-ECP 058 100 042 073B3LYP-dv 074 042 100 072B3LYP-ECP 037 073 072 100
computational methods (Table 6) only the energy order isperfectly reproduced by all the methods There is a veryhigh similarity in the order of HOMO and LUMO especiallyLUMO computed using B3LYP In addition B3LYP is foundto also perform better in reproducing the shielding tensors ofRu and other atoms compared to PBE except for the orderof the isotropic shielding of other atoms besides Ru atomThe correlation obtained fromB3LYP in computing shieldingtensors further supports its reported better performance forthese properties [42]
In computation of the 119869-coupling we are only limited toB3LYP and PBE since these properties are not permitted inGaussian package at MP2 and CCSD level of theories Con-sidering the magnitude of 119869-coupling at B3LYPDGDZVP itfollows the order Ru-P gt Ru-N gt Ru-Cl gt Ru-S gt Ru-O gtRu-C (Table 7) The order is well reproduced in B3LYP withECP basis set but is poor in PBE and is even the worst whenPBE is combined with ECP basis set (Table 8) The simplereason for the variations is in support of the literature reportdemonstrating that the 119869-coupling is sensitive to bondinginteractions [43]
33 Hyperpolarizability Properties The values of the com-puted hyperpolarizabilities of the six models using differentfunctionals and basis sets are shown in Table 9 The values ofthe hyperpolarizabilities of themodels usingMP2 functionalsat different basis sets are in the order of Ru-S gt Ru-O gt Ru-Cl gt Ru-N gt Ru-P gt Ru-C which suggest the level of theirpossible modelling for NLO application The order obtained
from CCSD is Ru-O gt Ru-Cl gt Ru-S gt Ru-P gt Ru-N gt Ru-C the PBE methods give the order Ru-Cl gt Ru-C lt Ru-S gtRu-O gt Ru-P gt Ru-N and B3LYP gives the order Ru-Cl gtRu-O gt Ru-S gt Ru-P gt Ru-N gt Ru-C The MP2 rated Ru-S as the best model for NLO application while CCSD ratedmodel Ru-O as the best Also a different model Ru-Cl isindicated to have the highest hyperpolarizabilities using thefunctionals PBE and B3LYP irrespective of the basis set usedThe correlations of the hyperpolarizabilities values among themodels are shown in Table 10 The correlation table showsthat the order of the hyperpolarizabilities of the models isperfectly reproducible using the same MP2 at different basissets and also within CCSD at different basis sets Also B3LYPperforms better in reproducing its order at different basisset compared to PBE This clearly shows that the order ofthe hyperpolarizabilities depends greatly on the geometricalconfiguration and the type of the functional used rather thanon the type of the basis sets The only observed similarity inthe order of the hyperpolarizabilities computed with differentmethods is that all the methods rated the models Ru-S Ru-Cl and Ru-O among the best three except for PBE whichexcluded Ru-O from its best three
34 The IR Vibrations The IR vibrations of the modelsat different computational methods are shown in Figure 3The vibrations which are of significant interest to us aretheir Ru-ligand bonds of Ru-C Ru-N Ru-O Ru-Cl Ru-Pand Ru-S which are shown in Table 11 Also most of theprominent vibrations are assigned as shown in Table 12 In
Journal of Chemistry 7
Table9Th
efirsth
yperpo
lariz
ability(szlig)inesu(1times10minus30)v
aluesa
tdifferentcom
putatio
nalm
etho
ds
MP2
aug-cc-pV
TZMP2
DGDZV
PMP2
SBK
JCVDZ
CCSD
DGDZV
PCC
SDSBK
JCVDZ
PBEDGDZV
PPB
ESB
KJCVDZ
B3LY
PDGDZV
PB3
LYPSB
KJCVDZ
Ru-C
153
179
171
108
098
244
028
055
055
Ru-N
569
224
380
105
109
077
063
076
062
Ru-O
3505
1791
1860
822
548
178
160
220
205
Ru-C
l1173
1440
1325
558
547
284
289
325
313
Ru-P
177
180
213
124
151
152
147
135
137
Ru-S
28214
33591
11477
8295
315
214
182
207
165
8 Journal of Chemistry
Table10Th
ecorrelationwith
inthed
ifferentm
etho
dsused
incompu
tingthefi
rsth
yperpo
lariz
abilitie
s
MP2
aug-cc-pV
TZMP2
DGDZV
PMP2
SBK
JCVDZ
CCSD
DGDZV
PCC
SDSBK
JCVDZ
PBEDGDZV
PPB
ESB
KJCVDZ
B3LY
PDGDZV
PB3
LYPSB
KJCVDZ
MP2
-acc
100
100
100
004
014
019
030
024
010
MP2
-dv
100
100
100
minus001
010
020
029
022
009
MP2
-ecp
100
100
100
minus005
006
019
027
019
006
CCSD
-dv
004
minus001
minus005
100
095
031
062
075
075
CCSD
-ECP
014
010
006
095
100
045
081
092
091
PBE-dv
019
020
019
031
045
100
042
051
053
PBE-EC
P030
029
027
062
081
042
100
097
095
B3LY
P-dv
024
022
019
075
092
051
097
100
099
B3LY
P-EC
P010
009
006
075
091
053
095
099
100
Journal of Chemistry 9
200 300 400 500 600 700200 300 400 500 600 700
200 300 400 500 600 700200 300 400 500 600 700
200 300 400 500 600 700200 300 400 500 600 700
Ru-C-MP2Ru-C-CCSD
Ru-C-PBE0Ru-C-B3LYP
Ru-N-MP2Ru-N-CCSD
Ru-N-PBE0Ru-N-B3LYP
Ru-O-MP2Ru-O-CCSD
Ru-O-PBE0Ru-O-B3LYP
Ru-Cl-MP2Ru-Cl-CCSD
Ru-Cl-PBE0Ru-Cl-B3LYP
Ru-P-MP2Ru-P-CCSD
Ru-P-PBE0Ru-P-B3LYP
Ru-S-MP2Ru-S-CCSD
Ru-S-PBE0Ru-S-B3LYP
Figure 3 The IR vibrations of the six models computed using MP2 (black) CCSD (red) PBE (green) and B3LYP (blue)
10 Journal of Chemistry
Table11Th
eIRvibrations
oftheR
u-Lbo
ndsa
tdifferentcom
putatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
6077
72349120573(H
RuH)120592(Ru-C)
5872
73346120592(Ru-C)
68224
195
120592(Ru-C)
63297
226
120573(H
RuH)120592(Ru-C)
50222
238
120591(H
RuCH
)120592(Ru-C)
53062
71120573(H
RuH)120592(Ru-C)
Ru-N
71899
977
120592(Ru-N)120592(Ru-H)
62352
1636120592(Ru-N)
66265
2879120573(H
RuH)120592(Ru-N)
71495
1013
120592(Ru-N)
48235
101120592(Ru-N)
49539
738
120592(Ru-N)
65608
137
120573(H
RuH)120592(Ru-N)
Ru-O
7178
11371
120592(Ru-O)
63412
1586120592(Ru-O)
70574
75120592(Ru-O)
68889
2395
120592(Ru-O)
Ru-C
l43529
2195
120592(Ru-Cl)
5913
3644
120592(Ru-Cl)
65732
376
120592(Ru-Cl)
32331
1022
120592(Ru-Cl)
4478
43433
120592(Ru-Cl)
Ru-P
28203
171
120592(Ru-P)
2393
9395
120592(Ru-P)
44535
232
120592(Ru-P)
2793
71025
o(Ru
HPH
)120592(Ru-P)
23442
711
o(Ru
HPH
)120592(Ru-P)
Ru-S
4119
4401
120592(Ru-S)
32619
424
120592(Ru-S)
3574
92496
o(Ru
HSH
)120592(Ru-S)
40866
311
120592(Ru-S)
37311
597
o(Ru
HSH
)120592(Ru-S)
38596
1999
120592(Ru-S)
120592isstr
etching120573isbend
ing120591istorsionalandoisou
t-of-p
lane
torsional
Journal of Chemistry 11
Table12Th
eassignm
ento
fthe
prom
inentIRvibrations
ofthem
odels
atdifferent
compu
tatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
346783
9624120573(H
RuH)120592(Ru-H)
386628
124120573(H
RuH)120573(H
RuH)
120592(C
H)120592(Ru-H)
381759
1510
1120573(H
RuH)120573(H
RuH)
120591(H
RuHC)
30511
103120592(C
H)o(Ru
HCH
)120592(C
H)
313241
8772
120592(C
H)120592(C
H)
344585
6003
120592(Ru-H)
326534
582120573(H
CH)120592(C
H)120592(Ru-H)
3044
61
5191120592(C
H)o(Ru
HCH
)120592(Ru-H)
306501
5614120573(H
RuH)120573(H
RuH)
o(Ru
HCH
)323718
7402120573(H
CH)120573(H
RuH)120592(C
H)
310576
7913
120573(H
RuH)120592(Ru-H)
29104116677
120592(C
H)120592(C
H)
299873
14381
120592(C
H)120592(C
H)
310607
10481120573(H
RuC)
120591(H
CRuH
)o(Ru
HCH
)230969
6851120573(H
RuH)120591(H
RuHC)
120592(Ru-H)
247128
4498120573(H
RuH)o(Ru
HCH
)120592(Ru-H)
240085
1095
1120592(C
H)
231944
1014
7120573(H
RuC)
o(RuH
CH)
207553
969120573(H
RuH)120573(H
RuH)
120592(Ru-H)120592(Ru-H)
232314
1296
8120592(C
H)
Ru-N
38020714205120573(H
RuH)120573(H
RuH)
120573(H
RuH)
401043
1231120573(H
RuH)120591(H
RuHN)
120592(N
H)
403478
11428120591(H
RuNH)o(Ru
HNH)
120592(N
H)
353289
10673120573(H
RuH)120573(H
RuH)
339019
20019
120592(N
H)120592(N
H)
347897
18119120573(H
RuH)120573(H
RuH)
120591(H
RuHN)120592(Ru-H)
347497
1866120573(H
RuH)120573(H
RuH)
120592(Ru-H)
331504
19282
120592(N
H)120592(N
H)
32687139839
120592(N
H)120592(N
H)
336728
2897
5120592(Ru-H)
332695
1499
5120573(H
RuH)o(Ru
HNH)
318372
37524
120592(N
H)120592(N
H)
293151
4214120592(Ru-H)120592(Ru-H)120592(N
H)
120592(N
H)
327085
3514120573(H
RuH)120591(H
RuHN)
120592(Ru-H)
2746
17455
o(Ru
HNH)120592(Ru-H)
120592(Ru-H)
238961
4007120573(H
RuH)120592(Ru-H)
207916
6108
120592(Ru-H)
199979
4338
120573(H
NH)
210524
6443
o(Ru
HNH)120592(N
H)
120592(Ru-H)
203734
6557
120592(Ru-H)
Ru-O
372613
2694
9120592(O
H)
380749
28041
o(Ru
HOH)120592(Ru-H)
389061
1005
o(Ru
HOH)120573(H
RuH)
3608772399
3120592(O
H)
275932
1407120573(H
RuH)o(Ru
HOH)
o(Ru
HOH)120592(Ru-H)
31079
1921120573(H
RuO)120573(H
RuH)
o(Ru
HOH)
370979
51891120573(H
RuO)120573(H
RuO)
327956
2992120573(H
RuH)120573(H
RuH)
18598
2333
120592(Ru-H)120592(Ru-H)
179443
2374120573(H
RuH)o(Ru
HOH)
120592(Ru-H)
291506
5502
o(Ru
HOH)120592(Ru-H)
120592(Ru-H)
220079
1599120573(H
RuH)o(Ru
HOH)
120592(Ru-H)120592(Ru-H)
1346
08
2894120592(Ru-H)120592(Ru-H)
125632
2895120592(Ru-H)120573(H
ORu
)260461
4569120592(O
H)120573(H
ORu
)203014
1588
120592(Ru-H)
112741
9479120573(H
RuH)120592(Ru-H)
120592(Ru-H)
109235
7374
120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
205106
3383120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
147934
29120592(Ru-H)120592(Ru-H)
Ru-C
l185546
2458
120592(Ru-H)
308667
1411120573(H
RuH)o(Ru
HClH)
120592(Ru-H)
30365123653
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
22088
2242
120592(Ru-H)
131751
3288
120592(Ru-H)
179947
2511
o(Ru
HClH)120592(Ru-H)
120592(Ru-H)
261179
3015
120592(Ru-H)120573(H
RuH)
210816
1124
120592(Ru-H)
114581
9421
120592(Ru-H)
121159
3269120573(H
RuH)120573(H
RuH)
120573(H
RuCl)
20399
3006120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
203112
1687
120592(Ru-H)
84759
3157
120592(Ru-H)
110861
7222
o(Ru
HClH)o(Ru
HClH)
120592(Ru-H)120573(H
RuCl)
131224
3565
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
147293
3151
120592(Ru-H)
79488
381
120573(H
RuH)
7687
2483120573(H
RuH)120592(Ru-H)
120592(Ru-H)120592(Ru-H)
109164
1501120592(Ru-H)120573(H
RuH)
11346
9195
3120573(H
RuH)
12 Journal of Chemistry
Table12C
ontin
ued
B3LY
PCC
SDMP2
PBE
Ru-P
384575
1547
120573(H
RuH)
40856716207120573(H
RuH)120591(H
RuPH
)o(Ru
HPH
)410148
11361120573(H
RuH)120573(H
RuH)
3509879645120573(H
RuH)120592(Ru-H)
296363
1457120573(H
RuH)120592(Ru-H)
328227
1508120573(H
RuH)120573(H
RuH)
120591(H
PRuH
)264975
4273
120573(H
RuP)120592(Ru-H)
246259
4871
120592(PH)120592(PH)
253628
4006
120592(PH)120592(PH)
261721
3138
120592(Ru-H)
262336
4752
120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
24307
5689
120592(PH)120592(PH)
250603
4624
120592(PH)120592(PH)
259379
3579
120573(H
RuP)
256933
4865120573(H
RuP)120573
(HRu
H)
238468
1306120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
245899
7096
120592(PH)120592(PH)
255419
4427120573(H
RuH)120591(H
PRuH
)120591(H
PRuH
)228633
8692
120573(H
RuH)120592(PH)
237354
92120592(PH)
Ru-S
265041
1308
120592(SH)
290793
378120573(H
RuH)120591(H
SRuH
)120592(Ru-H)120573(H
RuS)
417199
15487
o(Ru
HSH
)o(Ru
HSH
)120573(H
RuH)
34606
2384120573(H
RuH)120573(H
RuH)
120573(H
RuH)o(Ru
HSH
)
26342
1916
120573(H
RuH)120592(Ru-H)
188073
1685120573(H
RuH)120573(H
RuH)
120592(Ru-H)
28041
199265120573(H
RuS)120573
(HRu
H)
120573(H
RuH)120592(Ru-H)
258225
1254
120592(SH)
1913
1699
120592(Ru-H)
114853
2967120591(H
SRuH
)120592(SH)
120592(Ru-H)
2385442392374
120573(H
RuS)
21675
2604
120592(Ru-H)
121642
3386120592(Ru-H)120592(Ru-H)
109859
10132120573(H
RuH)120591(H
SRuH
)o(Ru
HSH
)120592(Ru-H)
225761
44894
120592(Ru-H)120573(H
RuH)
132047
3699120592(Ru-H)120592(Ru-H)
11086
11006120573(H
RuH)120592(Ru-H)
82534
331120591(H
SRuH
)120592(Ru-H)
120592(Ru-H)
210643
5205
120592(Ru-H)
8835
5098
o(Ru
HSH
)o(Ru
HSH
)120592(Ru-H)120592(Ru-H)
Journal of Chemistry 13
all the methods Ru-C Ru-N and Ru-O vibrations are withinthe range of 500 to 720 which is far higher than the rangeof vibrations of Ru-Cl Ru-P and Ru-S which are foundwithin the range of 224 to 658 Generally the order of Ru-L vibrations can be assumed as Ru-N gt Ru-O gt Ru-C gtRu-Cl gt Ru-S gt Ru-P (Table 11) The wavenumbers of thevibrations computed from the different methods appear to besignificantly different from each other in values and positions(Figure 3) The features of the IR spectra using MP2 andCCSD are very similar in the models Some vibration around291506 in model Ru-O 303651 in Ru-Cl and 238544 inRu-S are very prominent in MP2 methods compared to inany other methods or even absent in other methods Forinstance the bending of the angle of HRuS which is found tobe prominent in MP2 method is completely absent in othermethods (see Figure 3 and Table 12) The MP2 and CCSDshow strong vibrations within the range of 3800 to 4100 inmany of the models which are obviously absent in manyof the PBE and B3LYP methods Using the PED methodas implemented in VEDA package most of these vibrationsat high frequencies are a result of the torsional and out-of-plane vibration of H-Ru-X-H where X represents the typeof the model as shown in Table 12 In addition most of thebending vibrations which are determined by PBE and B3LYPfrom 2800 to 3800 in the models are also determined byMP2 and CCSD though some cases are at lower wavenumbercompared to PBE and B3LYP (Table 12) In the models Ru-Oand Ru-Cl PBE and B3LYP give priority to the OH and RuHvibrations respectively whileMP2 andCCSD give priority tothe torsional stretching and angle bending of their atoms
4 Conclusions
Six models of Ru-L bonds Ru-C Ru-N Ru-O Ru-Cl Ru-P and Ru-S are built to represent common rutheniumcomplexes and possible ruthenium-receptor interactionsThe reproducibility of their geometrical electronic spec-troscopic and conductive properties was investigated usingMP2 CCSD PBE and B3LYP functionals with differentcombination of basis sets Generally we observed that thereproducibility of most of the properties is much easier usingdifferent basis sets compared to using different functionalmethods as a result of significant geometrical changes whichis possible especially if there are many light atoms likehydrogen atoms as in themodelsThe order of the energy andthe thermodynamic properties are found to be reproducibleusing different functionalmethods and basis sets butHOMOLUMO 119869-coupling hyperpolarizabilities and isotropic andanisotropic shielding are found to depend more on the typeof the functional used rather than on the type of the basis setThe only significant similarity observed among the methodsapplied in computing hyperpolarizabilities is that they allrated models Ru-S Ru-Cl and Ru-O among their best threeThe optimized geometries and the thermodynamic proper-ties obtained from the functional PBE are found to be verysimilar to MP2 and perform better than B3LYP and CCSDwhich further give insight into many literaturesrsquo preferencefor PBE in optimizing metal complexes In computation ofthe isotropic and anisotropic shielding tensors B3LYP gives
values similar to MP2 and performs better than PBE The IRvibrations and assignment clearly show that the vibrationsobtained from the MP2 and CCSD methods are very similarand give preference to the torsional and bending vibrationsof the molecules over their stretching The order of the IRvibrations of the ruthenium-ligand bonds can be assumed asRu-N gt Ru-O gt Ru-C gt Ru-Cl gt Ru-S gt Ru-P
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
The authors gracefully acknowledged the financial support ofGovan Mbeki Research and Development Centre Universityof Fort Hare South Africa The CHPC in Republic ofSouth Africa is gracefully acknowledged for providing thecomputing facilities and some of the software used for thecomputation
References
[1] B Dutta R Scopelliti and K Severin ldquoSynthesis structure andreactivity of the methoxy-bridged dimer [CpandRu(120583-OMe)]
2
(Cpand = 1205785-1-methoxy-24-di-tert-butyl-3-neopentylcyclopenta-dienyl)rdquo Organometallics vol 27 no 3 pp 423ndash429 2008
[2] M A Furrer F Schmitt M Wiederkehr L Juillerat-Jeanneretand B Therrien ldquoCellular delivery of pyrenyl-arene rutheniumcomplexes by a water-soluble arene ruthenium metalla-cagerdquoDalton Transactions vol 41 no 24 pp 7201ndash7211 2012
[3] Q ZhouW Lei YChen et al ldquoRuthenium(II)-arene complexeswith strong fluorescence insight into the underlying mecha-nismrdquoChemistrymdashA European Journal vol 18 no 28 pp 8617ndash8621 2012
[4] L Bıro E Farkas and P Buglyo ldquoHydrolytic behaviour andchloride ion binding capability of [Ru(1205786 minus119901minus cym)(H
2O)3]2+
a solution equilibrium studyrdquoDalton Transactions vol 41 no 1pp 285ndash291 2012
[5] Y Boutadla D L Davies R C Jones and K Singh ldquoThescope of ambiphilic acetate-assisted cyclometallation with half-sandwich complexes of iridium rhodium and rutheniumrdquoChemistrymdashA European Journal vol 17 no 12 pp 3438ndash34482011
[6] Y F Han H Li Y Fei Y J Lin W Z Zhang and GX Jin ldquoSynthesis and structural characterization of binuclearhalf-sandwich iridium rhodium and ruthenium complexescontaining 441015840-dipyridyldisulfide (4DPDS) ligandsrdquo DaltonTransactions vol 39 no 30 pp 7119ndash7124 2010
[7] B Dutta B F Curchod P Campomanes et al ldquoReactions ofalkynes with [RuCl(cyclopentadienyl)] complexes the impor-tant first stepsrdquo ChemistrymdashA European Journal vol 16 no 28pp 8400ndash8409 2010
[8] M Jimenez-Tenorio M C Puerta P Valerga S MonchoG Ujaque and A Lledos ldquoProton-transfer reactions to half-sandwich ruthenium trihydride complexes bearing hemilabilePN ligands experimental and density functional theory stud-iesrdquo Inorganic Chemistry vol 49 no 13 pp 6035ndash6057 2010
14 Journal of Chemistry
[9] B Dutta C Scolaro R Scopelliti P J Dyson and K Sev-erin ldquoImportance of the 120587-ligand remarkable effect of thecyclopentadienyl ring on the cytotoxicity of ruthenium PTAcompoundsrdquoOrganometallics vol 27 no 7 pp 1355ndash1357 2008
[10] T Bugarcic A Habtemariam J Stepankova et al ldquoThe con-trasting chemistry and cancer cell cytotoxicity of bipyridineand bipyridinediol ruthenium(II) arene complexesrdquo InorganicChemistry vol 47 no 24 pp 11470ndash11486 2008
[11] M Castellano-Castillo H Kostrhunova V Marini et al ldquoBind-ing ofmismatch repair proteinMutS tomispairedDNA adductsof intercalating ruthenium(II) arene complexesrdquo Journal ofBiological Inorganic Chemistry vol 13 no 6 pp 993ndash999 2008
[12] S J Dougan A Habtemariam S E McHale S Parsons andP J Sadler ldquoCatalytic organometallic anticancer complexesrdquoProceedings of the National Academy of Sciences of the UnitedStates of America vol 105 no 33 pp 11628ndash11633 2008
[13] S J Dougan M Melchart A Habtemariam S Parsons and PJ Sadler ldquoPhenylazo-pyridine and phenylazo-pyrazole chloridoruthenium(II) arene complexes arene loss aquation and can-cer cell cytotoxicityrdquo Inorganic Chemistry vol 45 no 26 pp10882ndash10894 2006
[14] V Ritleng P Bertani M Pfeffer C Sirlin and J HirschingerldquoOptically active ortho-metalated half-sandwich rutheniumcomplexes solid-state NMR as a convenient tool to analyzemixtures of diastereomersrdquo Inorganic Chemistry vol 40 no 20pp 5117ndash5122 2001
[15] Y Sunada Y Hayashi H Kawaguchi and K TatsumildquoAlkynethiolato and alkyneselenolato rutheniumhalf-sandwichcomplexes Synthesis structures and reactions with (1205785ndashC5H5)2Zrrdquo Inorganic Chemistry vol 40 no 27 pp 7072ndash70782001
[16] K Yamanari R Ito S Yamamoto et al ldquoCyclic tetramerscomposed of rhodium(III) iridium(III) or ruthenium(II) half-sandwich and6-purinethionesrdquo Inorganic Chemistry vol 41 no25 pp 6824ndash6830 2002
[17] F Caruso M Rossi A Benson et al ldquoRuthenium-arenecomplexes of curcumin X-ray and density functional the-ory structure synthesis and spectroscopic characterizationin vitro antitumor activity and DNA docking studies of (p-cymene)Ru(curcuminato)chlorordquo Journal of Medicinal Chem-istry vol 55 no 3 pp 1072ndash1081 2012
[18] C Gossens I Tavernelli and U Rothlisberger ldquoBinding oforganometallic ruthenium(II) anticancer compounds to nucle-obases a computational studyrdquo Journal of Physical Chemistry Avol 113 no 43 pp 11888ndash11897 2009
[19] A M Pizarro A Habtemariam and P J Sadler ldquoActiva-tion mechanisms for organometallic anticancer complexesrdquoin Medicinal Organometallic Chemistry vol 32 of Topics inOrganometallic Chemistry pp 21ndash56 Springer Berlin Ger-many 2010
[20] I Turel and J Kljun ldquoInteractions of metal ions with DNAits constituents and derivatives which may be relevant foranticancer researchrdquoCurrent Topics inMedicinal Chemistry vol11 no 21 pp 2661ndash2687 2011
[21] G Gasser I Ott and N Metzler-Nolte ldquoOrganometallic anti-cancer compoundsrdquo Journal of Medicinal Chemistry vol 54 no1 pp 3ndash25 2011
[22] K J Kilpin S Crot T Riedel J A Kitchen and P JDyson ldquoRuthenium(II) and osmium(II) 123-triazolylideneorganometallics a preliminary investigation into the biologicalactivity of rsquoclickrsquo carbene complexesrdquo Dalton Transactions vol43 no 3 pp 1443ndash1448 2014
[23] A F A Peacock S Parsons and P J Sadler ldquoTuning thehydrolytic aqueous chemistry of osmium arene complexeswith NO-chelating ligands to achieve cancer cell cytotoxicityrdquoJournal of the American Chemical Society vol 129 no 11 pp3348ndash3357 2007
[24] A F A Peacock M Melchart R J Deeth A Habtemariam SParsons and P J Sadler ldquoOsmium(II) and ruthenium(II) arenemaltolato complexes rapid hydrolysis and nucleobase bindingrdquoChemistrymdashA European Journal vol 13 no 9 pp 2601ndash26132007
[25] F Pelletier V Comte A Massard et al ldquoDevelopment ofbimetallic titanoceneminusrutheniumminusarene complexes as anti-cancer agents relationships between structural and biologicalpropertiesrdquo Journal of Medicinal Chemistry vol 53 no 19 pp6923ndash6933 2010
[26] K J Kilpin and P J Dyson ldquoEnzyme inhibition by metalcomplexes concepts strategies and applicationsrdquo ChemicalScience vol 4 no 4 pp 1410ndash1419 2013
[27] G Gasser andNMetzler-Nolte ldquoThe potential of organometal-lic complexes in medicinal chemistryrdquo Current Opinion inChemical Biology vol 16 no 1-2 pp 84ndash91 2012
[28] I Turel J Kljun F Perdih et al ldquoFirst ruthenium organometal-lic complex of antibacterial agent ofloxacin Crystal structureand interactions with DNArdquo Inorganic Chemistry vol 49 no23 pp 10750ndash10752 2010
[29] C Adamo and V Barone ldquoToward reliable density functionalmethods without adjustable parameters the PBE0 modelrdquoJournal of Chemical Physics vol 110 no 13 pp 6158ndash6170 1999
[30] A D Becke ldquoDensity-functional thermochemistry IIIThe roleof exact exchangerdquoThe Journal of Chemical Physics vol 98 no7 article 5648 1993
[31] W J Stevens M Krauss H Basch and P G Jasien ldquoRelativisticcompact effective potentials and efficient shared-exponentbasis sets for the third- fourth- and fifth-row atomsrdquoCanadianJournal of Chemistry vol 70 no 2 pp 612ndash630 1992
[32] M J Frisch GW Trucks H B Schlegel et alOfficial Gaussian09 Literature Citation Gaussian Wallingford UK 2009
[33] D J Feller ldquoThe role of databases in support of computationalchemistry calculationsrdquo Journal of Computational Chemistryvol 17 no 13 pp 1571ndash1586 1996
[34] K L Schuchardt B T Didier T Elsethagen et al ldquoBasis setexchange a community database for computational sciencesrdquoJournal of Chemical Information andModeling vol 47 no 3 pp1045ndash1052 2007
[35] Y Liu C-G Liu S-L Sun G-C Yang and Y-Q QiuldquoRedox-switching second-order nonlinear optical responses ofNandNandN ruthenium complexesrdquo Computational and TheoreticalChemistry vol 979 pp 112ndash118 2012
[36] P S Liyanage R M de Silva and K M N de Silva ldquoNonlinearoptical (NLO) properties of novel organometallic complexeshigh accuracy density functional theory (DFT) calculationsrdquoJournal of Molecular Structure THEOCHEM vol 639 pp 195ndash201 2003
[37] MH Jamroz ldquoVibrational EnergyDistributionAnalysis VEDA4 ProgramrdquoWarsaw Poland 2004ndash2010 httpwwwsmmgpl
[38] M H Jamroz J C Dobrowolski and R Brzozowski ldquoVibra-tional modes of 26- 27- and 23-diisopropylnaphthalene ADFT studyrdquo Journal of Molecular Structure vol 787 no 1ndash3 pp172ndash183 2006
[39] M H Jamroz ldquoVibrational Energy Distribution Analysis(VEDA) scopes and limitationsrdquo Spectrochimica Acta AMolec-ular and Biomolecular Spectroscopy vol 114 pp 220ndash230 2013
Journal of Chemistry 15
[40] R Marchal P Carbonniere D Begue and C Pouchan ldquoStruc-tural and vibrational determination of small galliumndasharsenideclusters fromCCSD(T) andDFT calculationsrdquoChemical PhysicsLetters vol 453 no 1ndash3 pp 49ndash54 2008
[41] R Marchal P Carbonniere and C Pouchan ldquoStructural andvibrational properties prediction of Sn
119899Te119899clusters (n = 2ndash
8) using the GSAM approachrdquo Computational and TheoreticalChemistry vol 990 pp 100ndash105 2012
[42] T Helgaker M Jaszunski and M Pecul ldquoThe quantum-chemical calculation of NMR indirect spin-spin coupling con-stantsrdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 53 no 4 pp 249ndash268 2008
[43] F A Perras andD L Bryce ldquoTheoretical study of homonuclear Jcoupling between quadrupolar spins single-crystal DOR andJ-resolved NMRrdquo Journal of Magnetic Resonance vol 242 pp23ndash32 2014
[44] I D Burns A F Hill A J P White D J Williams and J DE T Wilton-Ely ldquoPolyazolyl chelate chemistry 61 bidentatecoordination of HB(pz)
3(pz = Pyrazol-1-yl) to ruthenium and
osmium crystal structure of [RuH(CO)(PPh3)2k2-HB(pz)
3]rdquo
Organometallics vol 17 no 8 pp 1552ndash1557 1998[45] M Al-Noaimi and M A AlDamen ldquoRuthenium complexes
incorporating azoimine and 120572-diamine based ligands synthe-sis crystal structure electrochemistry and DFT calculationrdquoInorganica Chimica Acta vol 387 pp 45ndash51 2012
[46] K Nakajima Y Ando H Mano and M Kojima ldquoPhotosub-stitution reactivity crystal structures and electrochemistry ofruthenium(II) (III) complexes containing tetradentate (O
2N2
S2N2 and P
2N2) Schiff base ligandsrdquo Inorganica Chimica Acta
vol 274 no 2 pp 184ndash191 1998[47] Z-L Lu K Eichele I Warad et al ldquoSupported organometal-
lic complexes XXXVIII [1] Bis(methoxyethyldimethlphos-phine)ruthenium(II) complexes as transfer hydrogenation cat-alystsrdquo Zeitschrift fur Anorganische und Allgemeine Chemie vol629 no 7-8 pp 1308ndash1315 2003
[48] R Gaur and L Mishra ldquoSynthesis and characterization ofRu(II)ndashDMSOndashClndashchalcone complexes DNA binding nucle-ase and topoisomerase II inhibitory activityrdquo Inorganic Chem-istry vol 51 no 5 pp 3059ndash3070 2012
[49] B Cebrian-Losantos E Reisner C R Kowol et al ldquoSynthesisand reactivity of the aquation product of the antitumor complextrans-[Ru IIICI
4(indazole)
2] minusrdquo Inorganic Chemistry vol 47 no
14 pp 6513ndash6523 2008[50] B T Rasley M Rapta and R J Kulawiec ldquoDiastereoselectivity
in enolate coordination in a new class of chiral rutheniumenolate complexesrdquo Organometallics vol 15 no 13 pp 2852ndash2854 1996
[51] S David R S Perkins F R Fronczek S Kasiri S S MandalandR S Srivastava ldquoSynthesis characterization and anticanceractivity of ruthenium-pyrazole complexesrdquo Journal of InorganicBiochemistry vol 111 pp 33ndash39 2012
[52] B Dutta E Solari S Gauthier R Scopelliti and K SeverinldquoRuthenium half-sandwich complexes with sterically demand-ing cyclopentadienyl ligandsrdquo Organometallics vol 26 no 19pp 4791ndash4799 2007
[53] G Turkoglu S Tampier F Strinitz F W Heinemann E Hub-ner and N Burzlaff ldquoRuthenium carbonyl complexes bearingbis(pyrazol-1-yl)carboxylato ligandsrdquo Organometallics vol 31no 6 pp 2166ndash2174 2012
[54] A K Renfrew A D Phillips E Tapavicza R ScopellitiU Rothlisberger and P J Dyson ldquoTuning the efficacy of
ruthenium(II)-arene (RAPTA) antitumor compounds with flu-orinated arene ligandsrdquo Organometallics vol 28 no 17 pp5061ndash5071 2009
[55] P M Jeffries R E Ellenwood and G S Girolami ldquoAnionicruthenium(II) alkyls with ancillary diene and dienyl ligandssynthesis and structures of [(12057821205782-C
7H8)RuMe
4]2minus and [(12057831205782-
C8H11)RuMe
3]2minusrdquo Inorganica Chimica Acta vol 361 no 1 pp
3165ndash3170 2008[56] B R James D Dolphin T W Leung F W B Einstein
and A C Willis ldquoPreparation and characterization of someruthenium(III) porphyrins including the crystal structure ofbromo(octaethylporphinato)(triphenylphosphine)ruthenium(III)rdquoCanadian Journal of Chemistry vol 62 no 7 pp 1238ndash12451984
[57] M Plois R Wolf W Hujo and S Grimme ldquoTowards reagentsfor bimetallic activation reactions polyhydride complexes withRu2H3 Ru2ZnH6 and Cu
2Ru2H6coresrdquo European Journal of
Inorganic Chemistry vol 2013 no 17 pp 3039ndash3048 2013[58] L Hintermann L Xiao A Labonne and U Englert
ldquo[CpRu(1205786-naphthalene)]PF6as precursor in complex synthesis
and catalysis with the cyclopentadienyl-ruthenium(II) cationrdquoOrganometallics vol 28 no 19 pp 5739ndash5748 2009
[59] I W Wyman K N Robertson T S Cameron J C SwartsandM A S Aquino ldquoSynthesis structure and electrochemistryof (ferrocene-2-propenoato-OO1015840)bis[12-bis(diphenylphosphi-no)ethane-PP1015840]ruthenium(II) hexafluorophosphaterdquo Inorgan-ica Chimica Acta vol 359 no 9 pp 3092ndash3096 2006
[60] C A Vock C Scolaro A D Phillips R Scopelliti G Sava andP J Dyson ldquoSynthesis characterization and in vitro evaluationof novel ruthenium(II) 1205786-arene imidazole complexesrdquo Journalof Medicinal Chemistry vol 49 no 18 pp 5552ndash5561 2006
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
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Carbohydrate Chemistry
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Advances in
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Chromatography Research International
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CatalystsJournal of
Journal of Chemistry 3
Ru-C-MP2
Ru-O-MP2
Ru-S-MP2Ru-P-MP2
Ru-Cl-MP2
Ru-N-MP2
Ru-C-CCSD Ru-N-CCSD
Ru-O-CCSD
Ru-S-CCSD
Ru-P-CCSDRu-Cl-CCSD
Ru-C-PBE0
Ru-N-PBE0 Ru-O-PBE0
Ru-S-PBE0Ru-P-PBE0
Ru-Cl-PBE0
Ru-C-B3LYP Ru-N-B3LYP
Ru-O-B3LYP
Ru-S-B3LYP
Ru-P-B3LYPRu-Cl-B3LYP
1964 1980 1949 1951 1839 1878
1834 2116 1864 1861 1850 1874
2210 2208 2171 2480 2437 2448
2397 2419 2228 2237 2216 2223
Figure 1The bond distances of the six models of Ru-L bonds obtained from the optimized geometries at MP2 CCSD PBE and B3LYP usingSBKJC VDZ basis set
Table 2 The bond distances and thermodynamic properties using MP2ECP method and the differences using other methods (energies inKJMol)
Methodbonds Distance Energy Zero energy Thermal energy Enthalpy Gibbs-free CV KJMol-K 119878 KJMol-KRu-C-MP2-ECP 19485 minus35376119864 + 05 minus35457119864 + 05 minus35455119864 + 05 minus35455119864 + 05 minus35464119864 + 05 00782 02901
Ru-N-MP2-ECP 18342 minus35376119864 + 05 minus35457119864 + 05 minus35455119864 + 05 minus35455119864 + 05 minus35464119864 + 05 00782 02901
Ru-O-MP2-ECP 18501 minus39584119864 + 05 minus39681119864 + 05 minus39679119864 + 05 minus39679119864 + 05 minus39688119864 + 05 00769 02940
Ru-Cl-MP2-ECP 21711 minus44927119864 + 05 minus45022119864 + 05 minus45021119864 + 05 minus45021119864 + 05 minus45029119864 + 05 00736 02927
Ru-P-MP2-ECP 23969 minus11493119864 + 06 minus11499119864 + 06 minus11499119864 + 06 minus11499119864 + 06 minus11500119864 + 06 00973 03293
Ru-S-MP2-ECP 22157 minus12964119864 + 06 minus12973119864 + 06 minus12972119864 + 06 minus12972119864 + 06 minus12973119864 + 06 00855 03188
Difference of the other methods fromMP2SBKJC VDZRu-C-PBE-ECP 00024 minus29890119864 + 03 minus19950119864 + 03 minus19946119864 + 03 minus19946119864 + 03 minus19955119864 + 03 00017 00032
Ru-N-PBE-ECP 00120 minus29890119864 + 03 minus19950119864 + 03 minus19946119864 + 03 minus19946119864 + 03 minus19955119864 + 03 00017 00032
Ru-O-PBE-ECP 00243 minus31318119864 + 03 minus19966119864 + 03 minus19970119864 + 03 minus19970119864 + 03 minus19959119864 + 03 minus00011 minus00037
Ru-Cl-PBE-ECP 03088 minus32116119864 + 03 minus21228119864 + 03 minus21223119864 + 03 minus21223119864 + 03 minus21231119864 + 03 00021 00027
Ru-P-PBE-ECP 00219 minus35356119864 + 03 minus27378119864 + 03 minus27373119864 + 03 minus27373119864 + 03 minus27386119864 + 03 00009 00043
Ru-S-PBE-ECP 00074 minus37839119864 + 03 minus28207119864 + 03 minus28208119864 + 03 minus28208119864 + 03 minus28202119864 + 03 00007 minus00019
Ru-C-B3LYP-ECP 00159 minus31831119864 + 03 minus21836119864 + 03 minus21828119864 + 03 minus21828119864 + 03 minus21844119864 + 03 00039 00055
Ru-N-B3LYP-ECP 00047 minus45407119864 + 04 minus44429119864 + 04 minus44429119864 + 04 minus44429119864 + 04 minus44429119864 + 04 minus00012 00010
Ru-O-B3LYP-ECP 00144 minus33288119864 + 03 minus21890119864 + 03 minus21893119864 + 03 minus21893119864 + 03 minus21884119864 + 03 00000 minus00028
Ru-Cl-B3LYP-ECP 00392 minus34479119864 + 03 minus23536119864 + 03 minus23531119864 + 03 minus23531119864 + 03 minus23540119864 + 03 00022 00031
Ru-P-B3LYP-ECP 00398 minus40797119864 + 03 minus32774119864 + 03 minus32764119864 + 03 minus32764119864 + 03 minus32788119864 + 03 00031 00081
Ru-S-B3LYP-ECP 00125 minus43126119864 + 03 minus33423119864 + 03 minus33431119864 + 03 minus33431119864 + 03 minus33414119864 + 03 minus00029 minus00057
Ru-C-CCSD-ECP 00316 minus21515119864 + 01 minus71138119864 + 01 minus69570119864 + 01 minus69570119864 + 01 minus72697119864 + 01 00075 00105
Ru-N-CCSD-ECP 00436 minus42095119864 + 04 minus42295119864 + 04 minus42294119864 + 04 minus42294119864 + 04 minus42295119864 + 04 00024 00047
Ru-O-CCSD-ECP 00109 minus16767119864 + 01 minus54986119864 + 01 minus54600119864 + 01 minus54600119864 + 01 minus54878119864 + 01 00037 00009
Ru-Cl-CCSD-ECP 00368 minus24604119864 + 01 minus65007119864 + 01 minus64330119864 + 01 minus64330119864 + 01 minus65559119864 + 01 00037 00041
Ru-P-CCSD-ECP 00512 minus14740119864 + 00 minus12560119864 + 02 minus12351119864 + 02 minus12351119864 + 02 minus12915119864 + 02 00066 00189
Ru-S-CCSD-ECP 00211 minus37429119864 + 01 minus98966119864 + 01 minus99562119864 + 01 minus99562119864 + 01 minus98230119864 + 01 minus00017 minus00045
above other functional methods Ru-C bond values of ourmodel are within the common experimental bond values forRu-C while the values obtained for other modelled bondsare little below the common experimental values If the bondvalues obtained using theMP2 are compared to the analyticalvalues the differences in the values of other computational
methods from MP2 are calculated using simple expression119883other minus119883MP2 and are presented in Table 2The differences inbond values obtained using PBE compared to the analyticalvalues fromMP2 are smaller inmagnitude compared to othermethods (Table 2) but the order of the bond distances in themodel was not perfectly reproduced as in B3LYP and CCSD
4 Journal of Chemistry
HH
H
H
H
H
HHH
H
H
Cl
S
OC
RuRu
Ru
RuRuRu
P
N
Figure 2 The superposition of different model of Ru-L bonds obtained using MP2 (green) CCSD (blue) PBE (yellow) and B3LYP (cyan)to determine the RMSD of the whole geometries after the optimization of their respective geometries
Table 3 The correlation of the values of energy and thermody-namics properties at MP2SBKJC VDZ with other computationalmethods
MP2-ECP PBE B3LYP CCSDRu-L-dist 100 100 100Energy 100 100 100Zero energy 100 100 100Thermal energy 100 100 100Enthalpy 100 100 100Gibbs-free 100 100 100CV 099 097 095Entropy 098 095 092
(Table 3) All the thermodynamic properties were computedat 298150 Kelvin and pressure 1 Atm The magnitude ofthe differences in thermodynamic properties (Table 2) showsthat CCSD and PBE give closer values to MP2 than B3LYPAlso considering the reproducibility of the order of bonddistances obtained from MP2 in the other methods all thecomputational methods produced a perfect order for thethermodynamic energies except PBE which gave a relativelybetter order for the CV and the entropy (Table 3) Thisis an indication that PBE performs better for geometricaloptimization and computation of thermodynamic propertieswhich agree well with the literatures that reported PBEcorrelation in combination with SBKJC VDZ ECP basis setas a good method for the optimization of metal complexes[40 41]The computed types of energies using othermethodsof computation are higher in negative values thanMP2 whiletheir bond distance CV and S are higher in positive valuesConsidering the RMSD of all the atoms in each of the modelsas shown in Table 4 and Figure 2 the optimized geometriesobtained for the models Ru-C Ru-O and Ru-S at variouscomputational methods are very similar to lower RMSDcompared to what was obtained for the models Ru-N Ru-Cl and Ru-P Also the RMSD of the optimized geometriesobtained from the functional PBE are lower than those
Table 4 The RMSD of the optimized geometries obtained fromother methods of computation from that obtained from MP2 usingSBKJC VDZ ECP basis set
B3LYP CCSD PBERu-C 0963 1347 0637Ru-N 1030 1032 1035Ru-O 0056 0072 0065Ru-Cl 1302 1030 1268Ru-P 1203 1221 1190Ru-S 0265 0266 0252
obtained from B3LYP and CCSD which further supportsPBE as a good method for the optimization of rutheniumcomplexes
32 Energy HOMO LUMO Shielding Tensors and J-Coupling The values of the energy HOMO LUMO andisotropic and anisotropic shielding computed atMP2aug-cc-pVTZ and the variations obtainedwhen computedwith othermethods are presented in Table 5 The shielding tensors werecomputed using Gauge-Independent Atomic Orbital (GIAO)method The values of the energy and the variation obtainedat different functional and basis sets show that variation in theenergy values using different functional is lower comparedto variation in the energy values using different basis setsThis is an indication that the energy values depend moreon the type of basis sets rather than on the type of thefunctional However the variation in the values of HOMOLUMO and isotropic and anisotropic shielding at differentfunctional methods shows that they depend more on thetype of the functional and the geometrical change rather thanon the type of the basis sets The difference in the valuesof HOMO LUMO and isotropic and anisotropic shieldingwithin MP2 methods at different basis set is lower comparedto changing the functional to PBE and B3LYP Also B3LYPseems to perform better than PBE as the differences obtainedat B3LYP are far lower compared to PBE Also consideringthe reproducibility of the order of these properties at different
Journal of Chemistry 5
Table 5The energy shielding tensors and 119869-coupling values usingMP2acc method and the differences using other computational methods(the energy values in Hartree)
Energy HOMO LUMO Ru-Iso Ru-Aniso X-Iso X-AnisoRu-C-MP2-acc minus440352 minus092 minus042 minus742180 1069111 minus14988 52269
Ru-N-MP2-acc minus441877 minus090 minus046 minus1176015 946597 minus82579 178860
Ru-O-MP2-acc minus443924 minus068 minus018 minus918858 846675 minus16694 119428
Ru-Cl-MP2-acc minus482319 minus062 minus020 minus1122411 1052228 29822 238476
Ru-P-MP2-acc minus470544 minus087 minus037 minus1359081 1488590 44861 4141
Ru-S-MP2-acc minus476385 minus061 minus016 minus313338 582699 minus80439 237577
000Ru-C-MP2-dv minus7849 000 000 26183 minus38901 1148 659
Ru-N-MP2-dv minus7926 000 minus001 71088 minus70110 3343 minus1344
Ru-O-MP2-dv minus7914 000 000 minus44694 minus39512 minus13768 24327
Ru-Cl-MP2-dv minus7924 000 000 minus37254 114475 minus19716 35479
Ru-P-MP2-dv minus7957 000 000 minus177917 246557 2518 minus037
Ru-S-MP2-dv minus7719 002 minus002 minus611650 135558 minus20580 35851
Ru-C-MP2-ECP 426878 000 minus001 596528 minus920085 1311 193
Ru-N-MP2- ECP 426800 000 000 960319 minus813149 7435 minus7455
Ru-O-MP2- ECP 426812 000 000 740324 minus715956 minus8299 15674
Ru-Cl-MP2- ECP 426802 000 000 914427 minus867435 minus16484 41130
Ru-P-MP2- ECP 426770 000 minus001 1093680 minus1218157 3260 minus1317
Ru-S-MP2- ECP 427007 003 minus003 149743 minus496580 13797 minus14494
Ru-C-PBE-dv minus8075 020 minus022 minus5106 minus767006 34929 minus46155
Ru-N-PBE-dv minus8156 018 minus020 629261 minus496409 52642 minus92641
Ru-O-PBE-dv minus8147 022 minus018 13816439 15984243 minus383942 413974
Ru-Cl-PBE-dv minus8176 015 minus018 10321955 13287550 minus491003 4370795
Ru-P-PBE-dv minus8201 021 minus021 16547451 37324221 374088 1446238
Ru-S-PBE-dv minus7973 018 minus019 10654331 10347455 minus659068 1230739
Ru-C-PBE-ECP 426764 021 minus021 663760 minus1027535 7597 minus17075
Ru-N-PBE-ECP 426681 018 minus020 1071404 minus884998 53035 minus93320
Ru-O-PBE-ECP 426690 022 minus018 minus3381033 38277943 minus3091812 35041247
Ru-Cl-PBE-ECP 426660 015 minus018 minus757542 2579402 27160896
Ru-P-PBE-ECP 426635 021 minus021 19109900 96261433
Ru-S-PBE-ECP 426863 018 minus019 9522596 32119344 11565209 35835334
Ru-C-B3LYP-dv minus8128 016 minus018 81227 minus588737 4860 minus12006
Ru-N-B3LYP-dv minus8211 013 minus017 431991 minus275591 45112 minus75540
Ru-O-B3LYP-dv minus8203 017 minus016 273324 minus381398 minus23391 6813
Ru-Cl-B3LYP-dv minus8246 012 minus016 254850 minus284675 minus265807 309548
Ru-P-B3LYP-dv minus8270 016 minus019 472561 minus646413 minus5451 9137
Ru-S-B3LYP-dv minus8041 014 minus017 minus225901 minus250444 30708 minus72243
Ru-C-B3LYP-ECP 426757 016 minus018 624966 minus1003953 4904 minus12301
Ru-N-B3LYP-ECP 426673 013 minus017 1040250 minus853188 45960 minus77145
Ru-O-B3LYP-ECP 426681 017 minus016 802053 minus780523 minus19773 minus244
Ru-Cl-B3LYP-ECP 426638 012 minus016 977624 minus948089 minus236464 264500
Ru-P-B3LYP-ECP 426614 016 minus018 1207902 minus1376028 minus4806 7968
Ru-S-B3LYP-ECP 426843 014 minus017 212424 minus536594 33276 minus74643
MP2-acc stands for MP2aug-cc-pVTZ MP2-dv stands for MP2DGDZVP MP2-ECP stands for MP2SBKJC VDZ PBE-dv stands for PBEDGDZVP PBE-ECP stands for PBESBKJC VDZ B3LYP-dv stands for B3LYPDGDZVP and B3LYP-ECP stands for B3LYPSBKJC VDZ
6 Journal of Chemistry
Table 6 Correlation of othermethods of computation with theMP2acc in computing energy HOMO LUMO and isotropic and anisotropicshielding
MP2DGDZVP MP2SBKJC VDZ PBEDGDZVP PBESBKJC VDZ B3LYPDGDZVP B3LYPSBKJC VDZEnergy 100 100 100 100 100 100
HOMO 100 100 099 099 099 099
LUMO 100 100 100 099 100 100
Ru-Iso 074 083 minus009 minus011 091 094
Ru-Aniso 095 097 051 050 084 082
X-Iso 098 098 067 minus051 minus016 minus012
X-Aniso 099 098 minus035 033 071 073
Table 7 119869-coupling of the Ru-L bonds at different level of computational methods
PBEDGDZVP PBESBKJC VDZ B3LYPDGDZVP B3LYPSBKJC VDZRu-C minus185119864 + 001 114119864 + 000 minus268119864 + 000 136119864 + 000
Ru-N minus146119864 + 001 753119864 minus 001 656119864 + 001 607119864 + 000
Ru-O 245119864 + 001 minus980119864 minus 001 249119864 + 001 minus117119864 + 000
Ru-Cl 472119864 + 001 563119864 + 000 476119864 + 001 590119864 + 000
Ru-P minus651119864 + 001 minus314119864 minus 001 minus714119864 + 001 minus500119864 minus 001
Ru-S minus752119864 minus 001 106119864 + 000 469119864 minus 001 135119864 + 000
Table 8 Correlation of 119869-coupling within the methods
PBEDGDZVP PBESBKJC VDZ B3LYPDGDZVP B3LYPSBKJC VDZPBE-dv 100 058 074 037PBE-ECP 058 100 042 073B3LYP-dv 074 042 100 072B3LYP-ECP 037 073 072 100
computational methods (Table 6) only the energy order isperfectly reproduced by all the methods There is a veryhigh similarity in the order of HOMO and LUMO especiallyLUMO computed using B3LYP In addition B3LYP is foundto also perform better in reproducing the shielding tensors ofRu and other atoms compared to PBE except for the orderof the isotropic shielding of other atoms besides Ru atomThe correlation obtained fromB3LYP in computing shieldingtensors further supports its reported better performance forthese properties [42]
In computation of the 119869-coupling we are only limited toB3LYP and PBE since these properties are not permitted inGaussian package at MP2 and CCSD level of theories Con-sidering the magnitude of 119869-coupling at B3LYPDGDZVP itfollows the order Ru-P gt Ru-N gt Ru-Cl gt Ru-S gt Ru-O gtRu-C (Table 7) The order is well reproduced in B3LYP withECP basis set but is poor in PBE and is even the worst whenPBE is combined with ECP basis set (Table 8) The simplereason for the variations is in support of the literature reportdemonstrating that the 119869-coupling is sensitive to bondinginteractions [43]
33 Hyperpolarizability Properties The values of the com-puted hyperpolarizabilities of the six models using differentfunctionals and basis sets are shown in Table 9 The values ofthe hyperpolarizabilities of themodels usingMP2 functionalsat different basis sets are in the order of Ru-S gt Ru-O gt Ru-Cl gt Ru-N gt Ru-P gt Ru-C which suggest the level of theirpossible modelling for NLO application The order obtained
from CCSD is Ru-O gt Ru-Cl gt Ru-S gt Ru-P gt Ru-N gt Ru-C the PBE methods give the order Ru-Cl gt Ru-C lt Ru-S gtRu-O gt Ru-P gt Ru-N and B3LYP gives the order Ru-Cl gtRu-O gt Ru-S gt Ru-P gt Ru-N gt Ru-C The MP2 rated Ru-S as the best model for NLO application while CCSD ratedmodel Ru-O as the best Also a different model Ru-Cl isindicated to have the highest hyperpolarizabilities using thefunctionals PBE and B3LYP irrespective of the basis set usedThe correlations of the hyperpolarizabilities values among themodels are shown in Table 10 The correlation table showsthat the order of the hyperpolarizabilities of the models isperfectly reproducible using the same MP2 at different basissets and also within CCSD at different basis sets Also B3LYPperforms better in reproducing its order at different basisset compared to PBE This clearly shows that the order ofthe hyperpolarizabilities depends greatly on the geometricalconfiguration and the type of the functional used rather thanon the type of the basis sets The only observed similarity inthe order of the hyperpolarizabilities computed with differentmethods is that all the methods rated the models Ru-S Ru-Cl and Ru-O among the best three except for PBE whichexcluded Ru-O from its best three
34 The IR Vibrations The IR vibrations of the modelsat different computational methods are shown in Figure 3The vibrations which are of significant interest to us aretheir Ru-ligand bonds of Ru-C Ru-N Ru-O Ru-Cl Ru-Pand Ru-S which are shown in Table 11 Also most of theprominent vibrations are assigned as shown in Table 12 In
Journal of Chemistry 7
Table9Th
efirsth
yperpo
lariz
ability(szlig)inesu(1times10minus30)v
aluesa
tdifferentcom
putatio
nalm
etho
ds
MP2
aug-cc-pV
TZMP2
DGDZV
PMP2
SBK
JCVDZ
CCSD
DGDZV
PCC
SDSBK
JCVDZ
PBEDGDZV
PPB
ESB
KJCVDZ
B3LY
PDGDZV
PB3
LYPSB
KJCVDZ
Ru-C
153
179
171
108
098
244
028
055
055
Ru-N
569
224
380
105
109
077
063
076
062
Ru-O
3505
1791
1860
822
548
178
160
220
205
Ru-C
l1173
1440
1325
558
547
284
289
325
313
Ru-P
177
180
213
124
151
152
147
135
137
Ru-S
28214
33591
11477
8295
315
214
182
207
165
8 Journal of Chemistry
Table10Th
ecorrelationwith
inthed
ifferentm
etho
dsused
incompu
tingthefi
rsth
yperpo
lariz
abilitie
s
MP2
aug-cc-pV
TZMP2
DGDZV
PMP2
SBK
JCVDZ
CCSD
DGDZV
PCC
SDSBK
JCVDZ
PBEDGDZV
PPB
ESB
KJCVDZ
B3LY
PDGDZV
PB3
LYPSB
KJCVDZ
MP2
-acc
100
100
100
004
014
019
030
024
010
MP2
-dv
100
100
100
minus001
010
020
029
022
009
MP2
-ecp
100
100
100
minus005
006
019
027
019
006
CCSD
-dv
004
minus001
minus005
100
095
031
062
075
075
CCSD
-ECP
014
010
006
095
100
045
081
092
091
PBE-dv
019
020
019
031
045
100
042
051
053
PBE-EC
P030
029
027
062
081
042
100
097
095
B3LY
P-dv
024
022
019
075
092
051
097
100
099
B3LY
P-EC
P010
009
006
075
091
053
095
099
100
Journal of Chemistry 9
200 300 400 500 600 700200 300 400 500 600 700
200 300 400 500 600 700200 300 400 500 600 700
200 300 400 500 600 700200 300 400 500 600 700
Ru-C-MP2Ru-C-CCSD
Ru-C-PBE0Ru-C-B3LYP
Ru-N-MP2Ru-N-CCSD
Ru-N-PBE0Ru-N-B3LYP
Ru-O-MP2Ru-O-CCSD
Ru-O-PBE0Ru-O-B3LYP
Ru-Cl-MP2Ru-Cl-CCSD
Ru-Cl-PBE0Ru-Cl-B3LYP
Ru-P-MP2Ru-P-CCSD
Ru-P-PBE0Ru-P-B3LYP
Ru-S-MP2Ru-S-CCSD
Ru-S-PBE0Ru-S-B3LYP
Figure 3 The IR vibrations of the six models computed using MP2 (black) CCSD (red) PBE (green) and B3LYP (blue)
10 Journal of Chemistry
Table11Th
eIRvibrations
oftheR
u-Lbo
ndsa
tdifferentcom
putatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
6077
72349120573(H
RuH)120592(Ru-C)
5872
73346120592(Ru-C)
68224
195
120592(Ru-C)
63297
226
120573(H
RuH)120592(Ru-C)
50222
238
120591(H
RuCH
)120592(Ru-C)
53062
71120573(H
RuH)120592(Ru-C)
Ru-N
71899
977
120592(Ru-N)120592(Ru-H)
62352
1636120592(Ru-N)
66265
2879120573(H
RuH)120592(Ru-N)
71495
1013
120592(Ru-N)
48235
101120592(Ru-N)
49539
738
120592(Ru-N)
65608
137
120573(H
RuH)120592(Ru-N)
Ru-O
7178
11371
120592(Ru-O)
63412
1586120592(Ru-O)
70574
75120592(Ru-O)
68889
2395
120592(Ru-O)
Ru-C
l43529
2195
120592(Ru-Cl)
5913
3644
120592(Ru-Cl)
65732
376
120592(Ru-Cl)
32331
1022
120592(Ru-Cl)
4478
43433
120592(Ru-Cl)
Ru-P
28203
171
120592(Ru-P)
2393
9395
120592(Ru-P)
44535
232
120592(Ru-P)
2793
71025
o(Ru
HPH
)120592(Ru-P)
23442
711
o(Ru
HPH
)120592(Ru-P)
Ru-S
4119
4401
120592(Ru-S)
32619
424
120592(Ru-S)
3574
92496
o(Ru
HSH
)120592(Ru-S)
40866
311
120592(Ru-S)
37311
597
o(Ru
HSH
)120592(Ru-S)
38596
1999
120592(Ru-S)
120592isstr
etching120573isbend
ing120591istorsionalandoisou
t-of-p
lane
torsional
Journal of Chemistry 11
Table12Th
eassignm
ento
fthe
prom
inentIRvibrations
ofthem
odels
atdifferent
compu
tatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
346783
9624120573(H
RuH)120592(Ru-H)
386628
124120573(H
RuH)120573(H
RuH)
120592(C
H)120592(Ru-H)
381759
1510
1120573(H
RuH)120573(H
RuH)
120591(H
RuHC)
30511
103120592(C
H)o(Ru
HCH
)120592(C
H)
313241
8772
120592(C
H)120592(C
H)
344585
6003
120592(Ru-H)
326534
582120573(H
CH)120592(C
H)120592(Ru-H)
3044
61
5191120592(C
H)o(Ru
HCH
)120592(Ru-H)
306501
5614120573(H
RuH)120573(H
RuH)
o(Ru
HCH
)323718
7402120573(H
CH)120573(H
RuH)120592(C
H)
310576
7913
120573(H
RuH)120592(Ru-H)
29104116677
120592(C
H)120592(C
H)
299873
14381
120592(C
H)120592(C
H)
310607
10481120573(H
RuC)
120591(H
CRuH
)o(Ru
HCH
)230969
6851120573(H
RuH)120591(H
RuHC)
120592(Ru-H)
247128
4498120573(H
RuH)o(Ru
HCH
)120592(Ru-H)
240085
1095
1120592(C
H)
231944
1014
7120573(H
RuC)
o(RuH
CH)
207553
969120573(H
RuH)120573(H
RuH)
120592(Ru-H)120592(Ru-H)
232314
1296
8120592(C
H)
Ru-N
38020714205120573(H
RuH)120573(H
RuH)
120573(H
RuH)
401043
1231120573(H
RuH)120591(H
RuHN)
120592(N
H)
403478
11428120591(H
RuNH)o(Ru
HNH)
120592(N
H)
353289
10673120573(H
RuH)120573(H
RuH)
339019
20019
120592(N
H)120592(N
H)
347897
18119120573(H
RuH)120573(H
RuH)
120591(H
RuHN)120592(Ru-H)
347497
1866120573(H
RuH)120573(H
RuH)
120592(Ru-H)
331504
19282
120592(N
H)120592(N
H)
32687139839
120592(N
H)120592(N
H)
336728
2897
5120592(Ru-H)
332695
1499
5120573(H
RuH)o(Ru
HNH)
318372
37524
120592(N
H)120592(N
H)
293151
4214120592(Ru-H)120592(Ru-H)120592(N
H)
120592(N
H)
327085
3514120573(H
RuH)120591(H
RuHN)
120592(Ru-H)
2746
17455
o(Ru
HNH)120592(Ru-H)
120592(Ru-H)
238961
4007120573(H
RuH)120592(Ru-H)
207916
6108
120592(Ru-H)
199979
4338
120573(H
NH)
210524
6443
o(Ru
HNH)120592(N
H)
120592(Ru-H)
203734
6557
120592(Ru-H)
Ru-O
372613
2694
9120592(O
H)
380749
28041
o(Ru
HOH)120592(Ru-H)
389061
1005
o(Ru
HOH)120573(H
RuH)
3608772399
3120592(O
H)
275932
1407120573(H
RuH)o(Ru
HOH)
o(Ru
HOH)120592(Ru-H)
31079
1921120573(H
RuO)120573(H
RuH)
o(Ru
HOH)
370979
51891120573(H
RuO)120573(H
RuO)
327956
2992120573(H
RuH)120573(H
RuH)
18598
2333
120592(Ru-H)120592(Ru-H)
179443
2374120573(H
RuH)o(Ru
HOH)
120592(Ru-H)
291506
5502
o(Ru
HOH)120592(Ru-H)
120592(Ru-H)
220079
1599120573(H
RuH)o(Ru
HOH)
120592(Ru-H)120592(Ru-H)
1346
08
2894120592(Ru-H)120592(Ru-H)
125632
2895120592(Ru-H)120573(H
ORu
)260461
4569120592(O
H)120573(H
ORu
)203014
1588
120592(Ru-H)
112741
9479120573(H
RuH)120592(Ru-H)
120592(Ru-H)
109235
7374
120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
205106
3383120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
147934
29120592(Ru-H)120592(Ru-H)
Ru-C
l185546
2458
120592(Ru-H)
308667
1411120573(H
RuH)o(Ru
HClH)
120592(Ru-H)
30365123653
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
22088
2242
120592(Ru-H)
131751
3288
120592(Ru-H)
179947
2511
o(Ru
HClH)120592(Ru-H)
120592(Ru-H)
261179
3015
120592(Ru-H)120573(H
RuH)
210816
1124
120592(Ru-H)
114581
9421
120592(Ru-H)
121159
3269120573(H
RuH)120573(H
RuH)
120573(H
RuCl)
20399
3006120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
203112
1687
120592(Ru-H)
84759
3157
120592(Ru-H)
110861
7222
o(Ru
HClH)o(Ru
HClH)
120592(Ru-H)120573(H
RuCl)
131224
3565
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
147293
3151
120592(Ru-H)
79488
381
120573(H
RuH)
7687
2483120573(H
RuH)120592(Ru-H)
120592(Ru-H)120592(Ru-H)
109164
1501120592(Ru-H)120573(H
RuH)
11346
9195
3120573(H
RuH)
12 Journal of Chemistry
Table12C
ontin
ued
B3LY
PCC
SDMP2
PBE
Ru-P
384575
1547
120573(H
RuH)
40856716207120573(H
RuH)120591(H
RuPH
)o(Ru
HPH
)410148
11361120573(H
RuH)120573(H
RuH)
3509879645120573(H
RuH)120592(Ru-H)
296363
1457120573(H
RuH)120592(Ru-H)
328227
1508120573(H
RuH)120573(H
RuH)
120591(H
PRuH
)264975
4273
120573(H
RuP)120592(Ru-H)
246259
4871
120592(PH)120592(PH)
253628
4006
120592(PH)120592(PH)
261721
3138
120592(Ru-H)
262336
4752
120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
24307
5689
120592(PH)120592(PH)
250603
4624
120592(PH)120592(PH)
259379
3579
120573(H
RuP)
256933
4865120573(H
RuP)120573
(HRu
H)
238468
1306120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
245899
7096
120592(PH)120592(PH)
255419
4427120573(H
RuH)120591(H
PRuH
)120591(H
PRuH
)228633
8692
120573(H
RuH)120592(PH)
237354
92120592(PH)
Ru-S
265041
1308
120592(SH)
290793
378120573(H
RuH)120591(H
SRuH
)120592(Ru-H)120573(H
RuS)
417199
15487
o(Ru
HSH
)o(Ru
HSH
)120573(H
RuH)
34606
2384120573(H
RuH)120573(H
RuH)
120573(H
RuH)o(Ru
HSH
)
26342
1916
120573(H
RuH)120592(Ru-H)
188073
1685120573(H
RuH)120573(H
RuH)
120592(Ru-H)
28041
199265120573(H
RuS)120573
(HRu
H)
120573(H
RuH)120592(Ru-H)
258225
1254
120592(SH)
1913
1699
120592(Ru-H)
114853
2967120591(H
SRuH
)120592(SH)
120592(Ru-H)
2385442392374
120573(H
RuS)
21675
2604
120592(Ru-H)
121642
3386120592(Ru-H)120592(Ru-H)
109859
10132120573(H
RuH)120591(H
SRuH
)o(Ru
HSH
)120592(Ru-H)
225761
44894
120592(Ru-H)120573(H
RuH)
132047
3699120592(Ru-H)120592(Ru-H)
11086
11006120573(H
RuH)120592(Ru-H)
82534
331120591(H
SRuH
)120592(Ru-H)
120592(Ru-H)
210643
5205
120592(Ru-H)
8835
5098
o(Ru
HSH
)o(Ru
HSH
)120592(Ru-H)120592(Ru-H)
Journal of Chemistry 13
all the methods Ru-C Ru-N and Ru-O vibrations are withinthe range of 500 to 720 which is far higher than the rangeof vibrations of Ru-Cl Ru-P and Ru-S which are foundwithin the range of 224 to 658 Generally the order of Ru-L vibrations can be assumed as Ru-N gt Ru-O gt Ru-C gtRu-Cl gt Ru-S gt Ru-P (Table 11) The wavenumbers of thevibrations computed from the different methods appear to besignificantly different from each other in values and positions(Figure 3) The features of the IR spectra using MP2 andCCSD are very similar in the models Some vibration around291506 in model Ru-O 303651 in Ru-Cl and 238544 inRu-S are very prominent in MP2 methods compared to inany other methods or even absent in other methods Forinstance the bending of the angle of HRuS which is found tobe prominent in MP2 method is completely absent in othermethods (see Figure 3 and Table 12) The MP2 and CCSDshow strong vibrations within the range of 3800 to 4100 inmany of the models which are obviously absent in manyof the PBE and B3LYP methods Using the PED methodas implemented in VEDA package most of these vibrationsat high frequencies are a result of the torsional and out-of-plane vibration of H-Ru-X-H where X represents the typeof the model as shown in Table 12 In addition most of thebending vibrations which are determined by PBE and B3LYPfrom 2800 to 3800 in the models are also determined byMP2 and CCSD though some cases are at lower wavenumbercompared to PBE and B3LYP (Table 12) In the models Ru-Oand Ru-Cl PBE and B3LYP give priority to the OH and RuHvibrations respectively whileMP2 andCCSD give priority tothe torsional stretching and angle bending of their atoms
4 Conclusions
Six models of Ru-L bonds Ru-C Ru-N Ru-O Ru-Cl Ru-P and Ru-S are built to represent common rutheniumcomplexes and possible ruthenium-receptor interactionsThe reproducibility of their geometrical electronic spec-troscopic and conductive properties was investigated usingMP2 CCSD PBE and B3LYP functionals with differentcombination of basis sets Generally we observed that thereproducibility of most of the properties is much easier usingdifferent basis sets compared to using different functionalmethods as a result of significant geometrical changes whichis possible especially if there are many light atoms likehydrogen atoms as in themodelsThe order of the energy andthe thermodynamic properties are found to be reproducibleusing different functionalmethods and basis sets butHOMOLUMO 119869-coupling hyperpolarizabilities and isotropic andanisotropic shielding are found to depend more on the typeof the functional used rather than on the type of the basis setThe only significant similarity observed among the methodsapplied in computing hyperpolarizabilities is that they allrated models Ru-S Ru-Cl and Ru-O among their best threeThe optimized geometries and the thermodynamic proper-ties obtained from the functional PBE are found to be verysimilar to MP2 and perform better than B3LYP and CCSDwhich further give insight into many literaturesrsquo preferencefor PBE in optimizing metal complexes In computation ofthe isotropic and anisotropic shielding tensors B3LYP gives
values similar to MP2 and performs better than PBE The IRvibrations and assignment clearly show that the vibrationsobtained from the MP2 and CCSD methods are very similarand give preference to the torsional and bending vibrationsof the molecules over their stretching The order of the IRvibrations of the ruthenium-ligand bonds can be assumed asRu-N gt Ru-O gt Ru-C gt Ru-Cl gt Ru-S gt Ru-P
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
The authors gracefully acknowledged the financial support ofGovan Mbeki Research and Development Centre Universityof Fort Hare South Africa The CHPC in Republic ofSouth Africa is gracefully acknowledged for providing thecomputing facilities and some of the software used for thecomputation
References
[1] B Dutta R Scopelliti and K Severin ldquoSynthesis structure andreactivity of the methoxy-bridged dimer [CpandRu(120583-OMe)]
2
(Cpand = 1205785-1-methoxy-24-di-tert-butyl-3-neopentylcyclopenta-dienyl)rdquo Organometallics vol 27 no 3 pp 423ndash429 2008
[2] M A Furrer F Schmitt M Wiederkehr L Juillerat-Jeanneretand B Therrien ldquoCellular delivery of pyrenyl-arene rutheniumcomplexes by a water-soluble arene ruthenium metalla-cagerdquoDalton Transactions vol 41 no 24 pp 7201ndash7211 2012
[3] Q ZhouW Lei YChen et al ldquoRuthenium(II)-arene complexeswith strong fluorescence insight into the underlying mecha-nismrdquoChemistrymdashA European Journal vol 18 no 28 pp 8617ndash8621 2012
[4] L Bıro E Farkas and P Buglyo ldquoHydrolytic behaviour andchloride ion binding capability of [Ru(1205786 minus119901minus cym)(H
2O)3]2+
a solution equilibrium studyrdquoDalton Transactions vol 41 no 1pp 285ndash291 2012
[5] Y Boutadla D L Davies R C Jones and K Singh ldquoThescope of ambiphilic acetate-assisted cyclometallation with half-sandwich complexes of iridium rhodium and rutheniumrdquoChemistrymdashA European Journal vol 17 no 12 pp 3438ndash34482011
[6] Y F Han H Li Y Fei Y J Lin W Z Zhang and GX Jin ldquoSynthesis and structural characterization of binuclearhalf-sandwich iridium rhodium and ruthenium complexescontaining 441015840-dipyridyldisulfide (4DPDS) ligandsrdquo DaltonTransactions vol 39 no 30 pp 7119ndash7124 2010
[7] B Dutta B F Curchod P Campomanes et al ldquoReactions ofalkynes with [RuCl(cyclopentadienyl)] complexes the impor-tant first stepsrdquo ChemistrymdashA European Journal vol 16 no 28pp 8400ndash8409 2010
[8] M Jimenez-Tenorio M C Puerta P Valerga S MonchoG Ujaque and A Lledos ldquoProton-transfer reactions to half-sandwich ruthenium trihydride complexes bearing hemilabilePN ligands experimental and density functional theory stud-iesrdquo Inorganic Chemistry vol 49 no 13 pp 6035ndash6057 2010
14 Journal of Chemistry
[9] B Dutta C Scolaro R Scopelliti P J Dyson and K Sev-erin ldquoImportance of the 120587-ligand remarkable effect of thecyclopentadienyl ring on the cytotoxicity of ruthenium PTAcompoundsrdquoOrganometallics vol 27 no 7 pp 1355ndash1357 2008
[10] T Bugarcic A Habtemariam J Stepankova et al ldquoThe con-trasting chemistry and cancer cell cytotoxicity of bipyridineand bipyridinediol ruthenium(II) arene complexesrdquo InorganicChemistry vol 47 no 24 pp 11470ndash11486 2008
[11] M Castellano-Castillo H Kostrhunova V Marini et al ldquoBind-ing ofmismatch repair proteinMutS tomispairedDNA adductsof intercalating ruthenium(II) arene complexesrdquo Journal ofBiological Inorganic Chemistry vol 13 no 6 pp 993ndash999 2008
[12] S J Dougan A Habtemariam S E McHale S Parsons andP J Sadler ldquoCatalytic organometallic anticancer complexesrdquoProceedings of the National Academy of Sciences of the UnitedStates of America vol 105 no 33 pp 11628ndash11633 2008
[13] S J Dougan M Melchart A Habtemariam S Parsons and PJ Sadler ldquoPhenylazo-pyridine and phenylazo-pyrazole chloridoruthenium(II) arene complexes arene loss aquation and can-cer cell cytotoxicityrdquo Inorganic Chemistry vol 45 no 26 pp10882ndash10894 2006
[14] V Ritleng P Bertani M Pfeffer C Sirlin and J HirschingerldquoOptically active ortho-metalated half-sandwich rutheniumcomplexes solid-state NMR as a convenient tool to analyzemixtures of diastereomersrdquo Inorganic Chemistry vol 40 no 20pp 5117ndash5122 2001
[15] Y Sunada Y Hayashi H Kawaguchi and K TatsumildquoAlkynethiolato and alkyneselenolato rutheniumhalf-sandwichcomplexes Synthesis structures and reactions with (1205785ndashC5H5)2Zrrdquo Inorganic Chemistry vol 40 no 27 pp 7072ndash70782001
[16] K Yamanari R Ito S Yamamoto et al ldquoCyclic tetramerscomposed of rhodium(III) iridium(III) or ruthenium(II) half-sandwich and6-purinethionesrdquo Inorganic Chemistry vol 41 no25 pp 6824ndash6830 2002
[17] F Caruso M Rossi A Benson et al ldquoRuthenium-arenecomplexes of curcumin X-ray and density functional the-ory structure synthesis and spectroscopic characterizationin vitro antitumor activity and DNA docking studies of (p-cymene)Ru(curcuminato)chlorordquo Journal of Medicinal Chem-istry vol 55 no 3 pp 1072ndash1081 2012
[18] C Gossens I Tavernelli and U Rothlisberger ldquoBinding oforganometallic ruthenium(II) anticancer compounds to nucle-obases a computational studyrdquo Journal of Physical Chemistry Avol 113 no 43 pp 11888ndash11897 2009
[19] A M Pizarro A Habtemariam and P J Sadler ldquoActiva-tion mechanisms for organometallic anticancer complexesrdquoin Medicinal Organometallic Chemistry vol 32 of Topics inOrganometallic Chemistry pp 21ndash56 Springer Berlin Ger-many 2010
[20] I Turel and J Kljun ldquoInteractions of metal ions with DNAits constituents and derivatives which may be relevant foranticancer researchrdquoCurrent Topics inMedicinal Chemistry vol11 no 21 pp 2661ndash2687 2011
[21] G Gasser I Ott and N Metzler-Nolte ldquoOrganometallic anti-cancer compoundsrdquo Journal of Medicinal Chemistry vol 54 no1 pp 3ndash25 2011
[22] K J Kilpin S Crot T Riedel J A Kitchen and P JDyson ldquoRuthenium(II) and osmium(II) 123-triazolylideneorganometallics a preliminary investigation into the biologicalactivity of rsquoclickrsquo carbene complexesrdquo Dalton Transactions vol43 no 3 pp 1443ndash1448 2014
[23] A F A Peacock S Parsons and P J Sadler ldquoTuning thehydrolytic aqueous chemistry of osmium arene complexeswith NO-chelating ligands to achieve cancer cell cytotoxicityrdquoJournal of the American Chemical Society vol 129 no 11 pp3348ndash3357 2007
[24] A F A Peacock M Melchart R J Deeth A Habtemariam SParsons and P J Sadler ldquoOsmium(II) and ruthenium(II) arenemaltolato complexes rapid hydrolysis and nucleobase bindingrdquoChemistrymdashA European Journal vol 13 no 9 pp 2601ndash26132007
[25] F Pelletier V Comte A Massard et al ldquoDevelopment ofbimetallic titanoceneminusrutheniumminusarene complexes as anti-cancer agents relationships between structural and biologicalpropertiesrdquo Journal of Medicinal Chemistry vol 53 no 19 pp6923ndash6933 2010
[26] K J Kilpin and P J Dyson ldquoEnzyme inhibition by metalcomplexes concepts strategies and applicationsrdquo ChemicalScience vol 4 no 4 pp 1410ndash1419 2013
[27] G Gasser andNMetzler-Nolte ldquoThe potential of organometal-lic complexes in medicinal chemistryrdquo Current Opinion inChemical Biology vol 16 no 1-2 pp 84ndash91 2012
[28] I Turel J Kljun F Perdih et al ldquoFirst ruthenium organometal-lic complex of antibacterial agent ofloxacin Crystal structureand interactions with DNArdquo Inorganic Chemistry vol 49 no23 pp 10750ndash10752 2010
[29] C Adamo and V Barone ldquoToward reliable density functionalmethods without adjustable parameters the PBE0 modelrdquoJournal of Chemical Physics vol 110 no 13 pp 6158ndash6170 1999
[30] A D Becke ldquoDensity-functional thermochemistry IIIThe roleof exact exchangerdquoThe Journal of Chemical Physics vol 98 no7 article 5648 1993
[31] W J Stevens M Krauss H Basch and P G Jasien ldquoRelativisticcompact effective potentials and efficient shared-exponentbasis sets for the third- fourth- and fifth-row atomsrdquoCanadianJournal of Chemistry vol 70 no 2 pp 612ndash630 1992
[32] M J Frisch GW Trucks H B Schlegel et alOfficial Gaussian09 Literature Citation Gaussian Wallingford UK 2009
[33] D J Feller ldquoThe role of databases in support of computationalchemistry calculationsrdquo Journal of Computational Chemistryvol 17 no 13 pp 1571ndash1586 1996
[34] K L Schuchardt B T Didier T Elsethagen et al ldquoBasis setexchange a community database for computational sciencesrdquoJournal of Chemical Information andModeling vol 47 no 3 pp1045ndash1052 2007
[35] Y Liu C-G Liu S-L Sun G-C Yang and Y-Q QiuldquoRedox-switching second-order nonlinear optical responses ofNandNandN ruthenium complexesrdquo Computational and TheoreticalChemistry vol 979 pp 112ndash118 2012
[36] P S Liyanage R M de Silva and K M N de Silva ldquoNonlinearoptical (NLO) properties of novel organometallic complexeshigh accuracy density functional theory (DFT) calculationsrdquoJournal of Molecular Structure THEOCHEM vol 639 pp 195ndash201 2003
[37] MH Jamroz ldquoVibrational EnergyDistributionAnalysis VEDA4 ProgramrdquoWarsaw Poland 2004ndash2010 httpwwwsmmgpl
[38] M H Jamroz J C Dobrowolski and R Brzozowski ldquoVibra-tional modes of 26- 27- and 23-diisopropylnaphthalene ADFT studyrdquo Journal of Molecular Structure vol 787 no 1ndash3 pp172ndash183 2006
[39] M H Jamroz ldquoVibrational Energy Distribution Analysis(VEDA) scopes and limitationsrdquo Spectrochimica Acta AMolec-ular and Biomolecular Spectroscopy vol 114 pp 220ndash230 2013
Journal of Chemistry 15
[40] R Marchal P Carbonniere D Begue and C Pouchan ldquoStruc-tural and vibrational determination of small galliumndasharsenideclusters fromCCSD(T) andDFT calculationsrdquoChemical PhysicsLetters vol 453 no 1ndash3 pp 49ndash54 2008
[41] R Marchal P Carbonniere and C Pouchan ldquoStructural andvibrational properties prediction of Sn
119899Te119899clusters (n = 2ndash
8) using the GSAM approachrdquo Computational and TheoreticalChemistry vol 990 pp 100ndash105 2012
[42] T Helgaker M Jaszunski and M Pecul ldquoThe quantum-chemical calculation of NMR indirect spin-spin coupling con-stantsrdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 53 no 4 pp 249ndash268 2008
[43] F A Perras andD L Bryce ldquoTheoretical study of homonuclear Jcoupling between quadrupolar spins single-crystal DOR andJ-resolved NMRrdquo Journal of Magnetic Resonance vol 242 pp23ndash32 2014
[44] I D Burns A F Hill A J P White D J Williams and J DE T Wilton-Ely ldquoPolyazolyl chelate chemistry 61 bidentatecoordination of HB(pz)
3(pz = Pyrazol-1-yl) to ruthenium and
osmium crystal structure of [RuH(CO)(PPh3)2k2-HB(pz)
3]rdquo
Organometallics vol 17 no 8 pp 1552ndash1557 1998[45] M Al-Noaimi and M A AlDamen ldquoRuthenium complexes
incorporating azoimine and 120572-diamine based ligands synthe-sis crystal structure electrochemistry and DFT calculationrdquoInorganica Chimica Acta vol 387 pp 45ndash51 2012
[46] K Nakajima Y Ando H Mano and M Kojima ldquoPhotosub-stitution reactivity crystal structures and electrochemistry ofruthenium(II) (III) complexes containing tetradentate (O
2N2
S2N2 and P
2N2) Schiff base ligandsrdquo Inorganica Chimica Acta
vol 274 no 2 pp 184ndash191 1998[47] Z-L Lu K Eichele I Warad et al ldquoSupported organometal-
lic complexes XXXVIII [1] Bis(methoxyethyldimethlphos-phine)ruthenium(II) complexes as transfer hydrogenation cat-alystsrdquo Zeitschrift fur Anorganische und Allgemeine Chemie vol629 no 7-8 pp 1308ndash1315 2003
[48] R Gaur and L Mishra ldquoSynthesis and characterization ofRu(II)ndashDMSOndashClndashchalcone complexes DNA binding nucle-ase and topoisomerase II inhibitory activityrdquo Inorganic Chem-istry vol 51 no 5 pp 3059ndash3070 2012
[49] B Cebrian-Losantos E Reisner C R Kowol et al ldquoSynthesisand reactivity of the aquation product of the antitumor complextrans-[Ru IIICI
4(indazole)
2] minusrdquo Inorganic Chemistry vol 47 no
14 pp 6513ndash6523 2008[50] B T Rasley M Rapta and R J Kulawiec ldquoDiastereoselectivity
in enolate coordination in a new class of chiral rutheniumenolate complexesrdquo Organometallics vol 15 no 13 pp 2852ndash2854 1996
[51] S David R S Perkins F R Fronczek S Kasiri S S MandalandR S Srivastava ldquoSynthesis characterization and anticanceractivity of ruthenium-pyrazole complexesrdquo Journal of InorganicBiochemistry vol 111 pp 33ndash39 2012
[52] B Dutta E Solari S Gauthier R Scopelliti and K SeverinldquoRuthenium half-sandwich complexes with sterically demand-ing cyclopentadienyl ligandsrdquo Organometallics vol 26 no 19pp 4791ndash4799 2007
[53] G Turkoglu S Tampier F Strinitz F W Heinemann E Hub-ner and N Burzlaff ldquoRuthenium carbonyl complexes bearingbis(pyrazol-1-yl)carboxylato ligandsrdquo Organometallics vol 31no 6 pp 2166ndash2174 2012
[54] A K Renfrew A D Phillips E Tapavicza R ScopellitiU Rothlisberger and P J Dyson ldquoTuning the efficacy of
ruthenium(II)-arene (RAPTA) antitumor compounds with flu-orinated arene ligandsrdquo Organometallics vol 28 no 17 pp5061ndash5071 2009
[55] P M Jeffries R E Ellenwood and G S Girolami ldquoAnionicruthenium(II) alkyls with ancillary diene and dienyl ligandssynthesis and structures of [(12057821205782-C
7H8)RuMe
4]2minus and [(12057831205782-
C8H11)RuMe
3]2minusrdquo Inorganica Chimica Acta vol 361 no 1 pp
3165ndash3170 2008[56] B R James D Dolphin T W Leung F W B Einstein
and A C Willis ldquoPreparation and characterization of someruthenium(III) porphyrins including the crystal structure ofbromo(octaethylporphinato)(triphenylphosphine)ruthenium(III)rdquoCanadian Journal of Chemistry vol 62 no 7 pp 1238ndash12451984
[57] M Plois R Wolf W Hujo and S Grimme ldquoTowards reagentsfor bimetallic activation reactions polyhydride complexes withRu2H3 Ru2ZnH6 and Cu
2Ru2H6coresrdquo European Journal of
Inorganic Chemistry vol 2013 no 17 pp 3039ndash3048 2013[58] L Hintermann L Xiao A Labonne and U Englert
ldquo[CpRu(1205786-naphthalene)]PF6as precursor in complex synthesis
and catalysis with the cyclopentadienyl-ruthenium(II) cationrdquoOrganometallics vol 28 no 19 pp 5739ndash5748 2009
[59] I W Wyman K N Robertson T S Cameron J C SwartsandM A S Aquino ldquoSynthesis structure and electrochemistryof (ferrocene-2-propenoato-OO1015840)bis[12-bis(diphenylphosphi-no)ethane-PP1015840]ruthenium(II) hexafluorophosphaterdquo Inorgan-ica Chimica Acta vol 359 no 9 pp 3092ndash3096 2006
[60] C A Vock C Scolaro A D Phillips R Scopelliti G Sava andP J Dyson ldquoSynthesis characterization and in vitro evaluationof novel ruthenium(II) 1205786-arene imidazole complexesrdquo Journalof Medicinal Chemistry vol 49 no 18 pp 5552ndash5561 2006
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
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Advances in
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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CatalystsJournal of
4 Journal of Chemistry
HH
H
H
H
H
HHH
H
H
Cl
S
OC
RuRu
Ru
RuRuRu
P
N
Figure 2 The superposition of different model of Ru-L bonds obtained using MP2 (green) CCSD (blue) PBE (yellow) and B3LYP (cyan)to determine the RMSD of the whole geometries after the optimization of their respective geometries
Table 3 The correlation of the values of energy and thermody-namics properties at MP2SBKJC VDZ with other computationalmethods
MP2-ECP PBE B3LYP CCSDRu-L-dist 100 100 100Energy 100 100 100Zero energy 100 100 100Thermal energy 100 100 100Enthalpy 100 100 100Gibbs-free 100 100 100CV 099 097 095Entropy 098 095 092
(Table 3) All the thermodynamic properties were computedat 298150 Kelvin and pressure 1 Atm The magnitude ofthe differences in thermodynamic properties (Table 2) showsthat CCSD and PBE give closer values to MP2 than B3LYPAlso considering the reproducibility of the order of bonddistances obtained from MP2 in the other methods all thecomputational methods produced a perfect order for thethermodynamic energies except PBE which gave a relativelybetter order for the CV and the entropy (Table 3) Thisis an indication that PBE performs better for geometricaloptimization and computation of thermodynamic propertieswhich agree well with the literatures that reported PBEcorrelation in combination with SBKJC VDZ ECP basis setas a good method for the optimization of metal complexes[40 41]The computed types of energies using othermethodsof computation are higher in negative values thanMP2 whiletheir bond distance CV and S are higher in positive valuesConsidering the RMSD of all the atoms in each of the modelsas shown in Table 4 and Figure 2 the optimized geometriesobtained for the models Ru-C Ru-O and Ru-S at variouscomputational methods are very similar to lower RMSDcompared to what was obtained for the models Ru-N Ru-Cl and Ru-P Also the RMSD of the optimized geometriesobtained from the functional PBE are lower than those
Table 4 The RMSD of the optimized geometries obtained fromother methods of computation from that obtained from MP2 usingSBKJC VDZ ECP basis set
B3LYP CCSD PBERu-C 0963 1347 0637Ru-N 1030 1032 1035Ru-O 0056 0072 0065Ru-Cl 1302 1030 1268Ru-P 1203 1221 1190Ru-S 0265 0266 0252
obtained from B3LYP and CCSD which further supportsPBE as a good method for the optimization of rutheniumcomplexes
32 Energy HOMO LUMO Shielding Tensors and J-Coupling The values of the energy HOMO LUMO andisotropic and anisotropic shielding computed atMP2aug-cc-pVTZ and the variations obtainedwhen computedwith othermethods are presented in Table 5 The shielding tensors werecomputed using Gauge-Independent Atomic Orbital (GIAO)method The values of the energy and the variation obtainedat different functional and basis sets show that variation in theenergy values using different functional is lower comparedto variation in the energy values using different basis setsThis is an indication that the energy values depend moreon the type of basis sets rather than on the type of thefunctional However the variation in the values of HOMOLUMO and isotropic and anisotropic shielding at differentfunctional methods shows that they depend more on thetype of the functional and the geometrical change rather thanon the type of the basis sets The difference in the valuesof HOMO LUMO and isotropic and anisotropic shieldingwithin MP2 methods at different basis set is lower comparedto changing the functional to PBE and B3LYP Also B3LYPseems to perform better than PBE as the differences obtainedat B3LYP are far lower compared to PBE Also consideringthe reproducibility of the order of these properties at different
Journal of Chemistry 5
Table 5The energy shielding tensors and 119869-coupling values usingMP2acc method and the differences using other computational methods(the energy values in Hartree)
Energy HOMO LUMO Ru-Iso Ru-Aniso X-Iso X-AnisoRu-C-MP2-acc minus440352 minus092 minus042 minus742180 1069111 minus14988 52269
Ru-N-MP2-acc minus441877 minus090 minus046 minus1176015 946597 minus82579 178860
Ru-O-MP2-acc minus443924 minus068 minus018 minus918858 846675 minus16694 119428
Ru-Cl-MP2-acc minus482319 minus062 minus020 minus1122411 1052228 29822 238476
Ru-P-MP2-acc minus470544 minus087 minus037 minus1359081 1488590 44861 4141
Ru-S-MP2-acc minus476385 minus061 minus016 minus313338 582699 minus80439 237577
000Ru-C-MP2-dv minus7849 000 000 26183 minus38901 1148 659
Ru-N-MP2-dv minus7926 000 minus001 71088 minus70110 3343 minus1344
Ru-O-MP2-dv minus7914 000 000 minus44694 minus39512 minus13768 24327
Ru-Cl-MP2-dv minus7924 000 000 minus37254 114475 minus19716 35479
Ru-P-MP2-dv minus7957 000 000 minus177917 246557 2518 minus037
Ru-S-MP2-dv minus7719 002 minus002 minus611650 135558 minus20580 35851
Ru-C-MP2-ECP 426878 000 minus001 596528 minus920085 1311 193
Ru-N-MP2- ECP 426800 000 000 960319 minus813149 7435 minus7455
Ru-O-MP2- ECP 426812 000 000 740324 minus715956 minus8299 15674
Ru-Cl-MP2- ECP 426802 000 000 914427 minus867435 minus16484 41130
Ru-P-MP2- ECP 426770 000 minus001 1093680 minus1218157 3260 minus1317
Ru-S-MP2- ECP 427007 003 minus003 149743 minus496580 13797 minus14494
Ru-C-PBE-dv minus8075 020 minus022 minus5106 minus767006 34929 minus46155
Ru-N-PBE-dv minus8156 018 minus020 629261 minus496409 52642 minus92641
Ru-O-PBE-dv minus8147 022 minus018 13816439 15984243 minus383942 413974
Ru-Cl-PBE-dv minus8176 015 minus018 10321955 13287550 minus491003 4370795
Ru-P-PBE-dv minus8201 021 minus021 16547451 37324221 374088 1446238
Ru-S-PBE-dv minus7973 018 minus019 10654331 10347455 minus659068 1230739
Ru-C-PBE-ECP 426764 021 minus021 663760 minus1027535 7597 minus17075
Ru-N-PBE-ECP 426681 018 minus020 1071404 minus884998 53035 minus93320
Ru-O-PBE-ECP 426690 022 minus018 minus3381033 38277943 minus3091812 35041247
Ru-Cl-PBE-ECP 426660 015 minus018 minus757542 2579402 27160896
Ru-P-PBE-ECP 426635 021 minus021 19109900 96261433
Ru-S-PBE-ECP 426863 018 minus019 9522596 32119344 11565209 35835334
Ru-C-B3LYP-dv minus8128 016 minus018 81227 minus588737 4860 minus12006
Ru-N-B3LYP-dv minus8211 013 minus017 431991 minus275591 45112 minus75540
Ru-O-B3LYP-dv minus8203 017 minus016 273324 minus381398 minus23391 6813
Ru-Cl-B3LYP-dv minus8246 012 minus016 254850 minus284675 minus265807 309548
Ru-P-B3LYP-dv minus8270 016 minus019 472561 minus646413 minus5451 9137
Ru-S-B3LYP-dv minus8041 014 minus017 minus225901 minus250444 30708 minus72243
Ru-C-B3LYP-ECP 426757 016 minus018 624966 minus1003953 4904 minus12301
Ru-N-B3LYP-ECP 426673 013 minus017 1040250 minus853188 45960 minus77145
Ru-O-B3LYP-ECP 426681 017 minus016 802053 minus780523 minus19773 minus244
Ru-Cl-B3LYP-ECP 426638 012 minus016 977624 minus948089 minus236464 264500
Ru-P-B3LYP-ECP 426614 016 minus018 1207902 minus1376028 minus4806 7968
Ru-S-B3LYP-ECP 426843 014 minus017 212424 minus536594 33276 minus74643
MP2-acc stands for MP2aug-cc-pVTZ MP2-dv stands for MP2DGDZVP MP2-ECP stands for MP2SBKJC VDZ PBE-dv stands for PBEDGDZVP PBE-ECP stands for PBESBKJC VDZ B3LYP-dv stands for B3LYPDGDZVP and B3LYP-ECP stands for B3LYPSBKJC VDZ
6 Journal of Chemistry
Table 6 Correlation of othermethods of computation with theMP2acc in computing energy HOMO LUMO and isotropic and anisotropicshielding
MP2DGDZVP MP2SBKJC VDZ PBEDGDZVP PBESBKJC VDZ B3LYPDGDZVP B3LYPSBKJC VDZEnergy 100 100 100 100 100 100
HOMO 100 100 099 099 099 099
LUMO 100 100 100 099 100 100
Ru-Iso 074 083 minus009 minus011 091 094
Ru-Aniso 095 097 051 050 084 082
X-Iso 098 098 067 minus051 minus016 minus012
X-Aniso 099 098 minus035 033 071 073
Table 7 119869-coupling of the Ru-L bonds at different level of computational methods
PBEDGDZVP PBESBKJC VDZ B3LYPDGDZVP B3LYPSBKJC VDZRu-C minus185119864 + 001 114119864 + 000 minus268119864 + 000 136119864 + 000
Ru-N minus146119864 + 001 753119864 minus 001 656119864 + 001 607119864 + 000
Ru-O 245119864 + 001 minus980119864 minus 001 249119864 + 001 minus117119864 + 000
Ru-Cl 472119864 + 001 563119864 + 000 476119864 + 001 590119864 + 000
Ru-P minus651119864 + 001 minus314119864 minus 001 minus714119864 + 001 minus500119864 minus 001
Ru-S minus752119864 minus 001 106119864 + 000 469119864 minus 001 135119864 + 000
Table 8 Correlation of 119869-coupling within the methods
PBEDGDZVP PBESBKJC VDZ B3LYPDGDZVP B3LYPSBKJC VDZPBE-dv 100 058 074 037PBE-ECP 058 100 042 073B3LYP-dv 074 042 100 072B3LYP-ECP 037 073 072 100
computational methods (Table 6) only the energy order isperfectly reproduced by all the methods There is a veryhigh similarity in the order of HOMO and LUMO especiallyLUMO computed using B3LYP In addition B3LYP is foundto also perform better in reproducing the shielding tensors ofRu and other atoms compared to PBE except for the orderof the isotropic shielding of other atoms besides Ru atomThe correlation obtained fromB3LYP in computing shieldingtensors further supports its reported better performance forthese properties [42]
In computation of the 119869-coupling we are only limited toB3LYP and PBE since these properties are not permitted inGaussian package at MP2 and CCSD level of theories Con-sidering the magnitude of 119869-coupling at B3LYPDGDZVP itfollows the order Ru-P gt Ru-N gt Ru-Cl gt Ru-S gt Ru-O gtRu-C (Table 7) The order is well reproduced in B3LYP withECP basis set but is poor in PBE and is even the worst whenPBE is combined with ECP basis set (Table 8) The simplereason for the variations is in support of the literature reportdemonstrating that the 119869-coupling is sensitive to bondinginteractions [43]
33 Hyperpolarizability Properties The values of the com-puted hyperpolarizabilities of the six models using differentfunctionals and basis sets are shown in Table 9 The values ofthe hyperpolarizabilities of themodels usingMP2 functionalsat different basis sets are in the order of Ru-S gt Ru-O gt Ru-Cl gt Ru-N gt Ru-P gt Ru-C which suggest the level of theirpossible modelling for NLO application The order obtained
from CCSD is Ru-O gt Ru-Cl gt Ru-S gt Ru-P gt Ru-N gt Ru-C the PBE methods give the order Ru-Cl gt Ru-C lt Ru-S gtRu-O gt Ru-P gt Ru-N and B3LYP gives the order Ru-Cl gtRu-O gt Ru-S gt Ru-P gt Ru-N gt Ru-C The MP2 rated Ru-S as the best model for NLO application while CCSD ratedmodel Ru-O as the best Also a different model Ru-Cl isindicated to have the highest hyperpolarizabilities using thefunctionals PBE and B3LYP irrespective of the basis set usedThe correlations of the hyperpolarizabilities values among themodels are shown in Table 10 The correlation table showsthat the order of the hyperpolarizabilities of the models isperfectly reproducible using the same MP2 at different basissets and also within CCSD at different basis sets Also B3LYPperforms better in reproducing its order at different basisset compared to PBE This clearly shows that the order ofthe hyperpolarizabilities depends greatly on the geometricalconfiguration and the type of the functional used rather thanon the type of the basis sets The only observed similarity inthe order of the hyperpolarizabilities computed with differentmethods is that all the methods rated the models Ru-S Ru-Cl and Ru-O among the best three except for PBE whichexcluded Ru-O from its best three
34 The IR Vibrations The IR vibrations of the modelsat different computational methods are shown in Figure 3The vibrations which are of significant interest to us aretheir Ru-ligand bonds of Ru-C Ru-N Ru-O Ru-Cl Ru-Pand Ru-S which are shown in Table 11 Also most of theprominent vibrations are assigned as shown in Table 12 In
Journal of Chemistry 7
Table9Th
efirsth
yperpo
lariz
ability(szlig)inesu(1times10minus30)v
aluesa
tdifferentcom
putatio
nalm
etho
ds
MP2
aug-cc-pV
TZMP2
DGDZV
PMP2
SBK
JCVDZ
CCSD
DGDZV
PCC
SDSBK
JCVDZ
PBEDGDZV
PPB
ESB
KJCVDZ
B3LY
PDGDZV
PB3
LYPSB
KJCVDZ
Ru-C
153
179
171
108
098
244
028
055
055
Ru-N
569
224
380
105
109
077
063
076
062
Ru-O
3505
1791
1860
822
548
178
160
220
205
Ru-C
l1173
1440
1325
558
547
284
289
325
313
Ru-P
177
180
213
124
151
152
147
135
137
Ru-S
28214
33591
11477
8295
315
214
182
207
165
8 Journal of Chemistry
Table10Th
ecorrelationwith
inthed
ifferentm
etho
dsused
incompu
tingthefi
rsth
yperpo
lariz
abilitie
s
MP2
aug-cc-pV
TZMP2
DGDZV
PMP2
SBK
JCVDZ
CCSD
DGDZV
PCC
SDSBK
JCVDZ
PBEDGDZV
PPB
ESB
KJCVDZ
B3LY
PDGDZV
PB3
LYPSB
KJCVDZ
MP2
-acc
100
100
100
004
014
019
030
024
010
MP2
-dv
100
100
100
minus001
010
020
029
022
009
MP2
-ecp
100
100
100
minus005
006
019
027
019
006
CCSD
-dv
004
minus001
minus005
100
095
031
062
075
075
CCSD
-ECP
014
010
006
095
100
045
081
092
091
PBE-dv
019
020
019
031
045
100
042
051
053
PBE-EC
P030
029
027
062
081
042
100
097
095
B3LY
P-dv
024
022
019
075
092
051
097
100
099
B3LY
P-EC
P010
009
006
075
091
053
095
099
100
Journal of Chemistry 9
200 300 400 500 600 700200 300 400 500 600 700
200 300 400 500 600 700200 300 400 500 600 700
200 300 400 500 600 700200 300 400 500 600 700
Ru-C-MP2Ru-C-CCSD
Ru-C-PBE0Ru-C-B3LYP
Ru-N-MP2Ru-N-CCSD
Ru-N-PBE0Ru-N-B3LYP
Ru-O-MP2Ru-O-CCSD
Ru-O-PBE0Ru-O-B3LYP
Ru-Cl-MP2Ru-Cl-CCSD
Ru-Cl-PBE0Ru-Cl-B3LYP
Ru-P-MP2Ru-P-CCSD
Ru-P-PBE0Ru-P-B3LYP
Ru-S-MP2Ru-S-CCSD
Ru-S-PBE0Ru-S-B3LYP
Figure 3 The IR vibrations of the six models computed using MP2 (black) CCSD (red) PBE (green) and B3LYP (blue)
10 Journal of Chemistry
Table11Th
eIRvibrations
oftheR
u-Lbo
ndsa
tdifferentcom
putatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
6077
72349120573(H
RuH)120592(Ru-C)
5872
73346120592(Ru-C)
68224
195
120592(Ru-C)
63297
226
120573(H
RuH)120592(Ru-C)
50222
238
120591(H
RuCH
)120592(Ru-C)
53062
71120573(H
RuH)120592(Ru-C)
Ru-N
71899
977
120592(Ru-N)120592(Ru-H)
62352
1636120592(Ru-N)
66265
2879120573(H
RuH)120592(Ru-N)
71495
1013
120592(Ru-N)
48235
101120592(Ru-N)
49539
738
120592(Ru-N)
65608
137
120573(H
RuH)120592(Ru-N)
Ru-O
7178
11371
120592(Ru-O)
63412
1586120592(Ru-O)
70574
75120592(Ru-O)
68889
2395
120592(Ru-O)
Ru-C
l43529
2195
120592(Ru-Cl)
5913
3644
120592(Ru-Cl)
65732
376
120592(Ru-Cl)
32331
1022
120592(Ru-Cl)
4478
43433
120592(Ru-Cl)
Ru-P
28203
171
120592(Ru-P)
2393
9395
120592(Ru-P)
44535
232
120592(Ru-P)
2793
71025
o(Ru
HPH
)120592(Ru-P)
23442
711
o(Ru
HPH
)120592(Ru-P)
Ru-S
4119
4401
120592(Ru-S)
32619
424
120592(Ru-S)
3574
92496
o(Ru
HSH
)120592(Ru-S)
40866
311
120592(Ru-S)
37311
597
o(Ru
HSH
)120592(Ru-S)
38596
1999
120592(Ru-S)
120592isstr
etching120573isbend
ing120591istorsionalandoisou
t-of-p
lane
torsional
Journal of Chemistry 11
Table12Th
eassignm
ento
fthe
prom
inentIRvibrations
ofthem
odels
atdifferent
compu
tatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
346783
9624120573(H
RuH)120592(Ru-H)
386628
124120573(H
RuH)120573(H
RuH)
120592(C
H)120592(Ru-H)
381759
1510
1120573(H
RuH)120573(H
RuH)
120591(H
RuHC)
30511
103120592(C
H)o(Ru
HCH
)120592(C
H)
313241
8772
120592(C
H)120592(C
H)
344585
6003
120592(Ru-H)
326534
582120573(H
CH)120592(C
H)120592(Ru-H)
3044
61
5191120592(C
H)o(Ru
HCH
)120592(Ru-H)
306501
5614120573(H
RuH)120573(H
RuH)
o(Ru
HCH
)323718
7402120573(H
CH)120573(H
RuH)120592(C
H)
310576
7913
120573(H
RuH)120592(Ru-H)
29104116677
120592(C
H)120592(C
H)
299873
14381
120592(C
H)120592(C
H)
310607
10481120573(H
RuC)
120591(H
CRuH
)o(Ru
HCH
)230969
6851120573(H
RuH)120591(H
RuHC)
120592(Ru-H)
247128
4498120573(H
RuH)o(Ru
HCH
)120592(Ru-H)
240085
1095
1120592(C
H)
231944
1014
7120573(H
RuC)
o(RuH
CH)
207553
969120573(H
RuH)120573(H
RuH)
120592(Ru-H)120592(Ru-H)
232314
1296
8120592(C
H)
Ru-N
38020714205120573(H
RuH)120573(H
RuH)
120573(H
RuH)
401043
1231120573(H
RuH)120591(H
RuHN)
120592(N
H)
403478
11428120591(H
RuNH)o(Ru
HNH)
120592(N
H)
353289
10673120573(H
RuH)120573(H
RuH)
339019
20019
120592(N
H)120592(N
H)
347897
18119120573(H
RuH)120573(H
RuH)
120591(H
RuHN)120592(Ru-H)
347497
1866120573(H
RuH)120573(H
RuH)
120592(Ru-H)
331504
19282
120592(N
H)120592(N
H)
32687139839
120592(N
H)120592(N
H)
336728
2897
5120592(Ru-H)
332695
1499
5120573(H
RuH)o(Ru
HNH)
318372
37524
120592(N
H)120592(N
H)
293151
4214120592(Ru-H)120592(Ru-H)120592(N
H)
120592(N
H)
327085
3514120573(H
RuH)120591(H
RuHN)
120592(Ru-H)
2746
17455
o(Ru
HNH)120592(Ru-H)
120592(Ru-H)
238961
4007120573(H
RuH)120592(Ru-H)
207916
6108
120592(Ru-H)
199979
4338
120573(H
NH)
210524
6443
o(Ru
HNH)120592(N
H)
120592(Ru-H)
203734
6557
120592(Ru-H)
Ru-O
372613
2694
9120592(O
H)
380749
28041
o(Ru
HOH)120592(Ru-H)
389061
1005
o(Ru
HOH)120573(H
RuH)
3608772399
3120592(O
H)
275932
1407120573(H
RuH)o(Ru
HOH)
o(Ru
HOH)120592(Ru-H)
31079
1921120573(H
RuO)120573(H
RuH)
o(Ru
HOH)
370979
51891120573(H
RuO)120573(H
RuO)
327956
2992120573(H
RuH)120573(H
RuH)
18598
2333
120592(Ru-H)120592(Ru-H)
179443
2374120573(H
RuH)o(Ru
HOH)
120592(Ru-H)
291506
5502
o(Ru
HOH)120592(Ru-H)
120592(Ru-H)
220079
1599120573(H
RuH)o(Ru
HOH)
120592(Ru-H)120592(Ru-H)
1346
08
2894120592(Ru-H)120592(Ru-H)
125632
2895120592(Ru-H)120573(H
ORu
)260461
4569120592(O
H)120573(H
ORu
)203014
1588
120592(Ru-H)
112741
9479120573(H
RuH)120592(Ru-H)
120592(Ru-H)
109235
7374
120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
205106
3383120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
147934
29120592(Ru-H)120592(Ru-H)
Ru-C
l185546
2458
120592(Ru-H)
308667
1411120573(H
RuH)o(Ru
HClH)
120592(Ru-H)
30365123653
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
22088
2242
120592(Ru-H)
131751
3288
120592(Ru-H)
179947
2511
o(Ru
HClH)120592(Ru-H)
120592(Ru-H)
261179
3015
120592(Ru-H)120573(H
RuH)
210816
1124
120592(Ru-H)
114581
9421
120592(Ru-H)
121159
3269120573(H
RuH)120573(H
RuH)
120573(H
RuCl)
20399
3006120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
203112
1687
120592(Ru-H)
84759
3157
120592(Ru-H)
110861
7222
o(Ru
HClH)o(Ru
HClH)
120592(Ru-H)120573(H
RuCl)
131224
3565
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
147293
3151
120592(Ru-H)
79488
381
120573(H
RuH)
7687
2483120573(H
RuH)120592(Ru-H)
120592(Ru-H)120592(Ru-H)
109164
1501120592(Ru-H)120573(H
RuH)
11346
9195
3120573(H
RuH)
12 Journal of Chemistry
Table12C
ontin
ued
B3LY
PCC
SDMP2
PBE
Ru-P
384575
1547
120573(H
RuH)
40856716207120573(H
RuH)120591(H
RuPH
)o(Ru
HPH
)410148
11361120573(H
RuH)120573(H
RuH)
3509879645120573(H
RuH)120592(Ru-H)
296363
1457120573(H
RuH)120592(Ru-H)
328227
1508120573(H
RuH)120573(H
RuH)
120591(H
PRuH
)264975
4273
120573(H
RuP)120592(Ru-H)
246259
4871
120592(PH)120592(PH)
253628
4006
120592(PH)120592(PH)
261721
3138
120592(Ru-H)
262336
4752
120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
24307
5689
120592(PH)120592(PH)
250603
4624
120592(PH)120592(PH)
259379
3579
120573(H
RuP)
256933
4865120573(H
RuP)120573
(HRu
H)
238468
1306120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
245899
7096
120592(PH)120592(PH)
255419
4427120573(H
RuH)120591(H
PRuH
)120591(H
PRuH
)228633
8692
120573(H
RuH)120592(PH)
237354
92120592(PH)
Ru-S
265041
1308
120592(SH)
290793
378120573(H
RuH)120591(H
SRuH
)120592(Ru-H)120573(H
RuS)
417199
15487
o(Ru
HSH
)o(Ru
HSH
)120573(H
RuH)
34606
2384120573(H
RuH)120573(H
RuH)
120573(H
RuH)o(Ru
HSH
)
26342
1916
120573(H
RuH)120592(Ru-H)
188073
1685120573(H
RuH)120573(H
RuH)
120592(Ru-H)
28041
199265120573(H
RuS)120573
(HRu
H)
120573(H
RuH)120592(Ru-H)
258225
1254
120592(SH)
1913
1699
120592(Ru-H)
114853
2967120591(H
SRuH
)120592(SH)
120592(Ru-H)
2385442392374
120573(H
RuS)
21675
2604
120592(Ru-H)
121642
3386120592(Ru-H)120592(Ru-H)
109859
10132120573(H
RuH)120591(H
SRuH
)o(Ru
HSH
)120592(Ru-H)
225761
44894
120592(Ru-H)120573(H
RuH)
132047
3699120592(Ru-H)120592(Ru-H)
11086
11006120573(H
RuH)120592(Ru-H)
82534
331120591(H
SRuH
)120592(Ru-H)
120592(Ru-H)
210643
5205
120592(Ru-H)
8835
5098
o(Ru
HSH
)o(Ru
HSH
)120592(Ru-H)120592(Ru-H)
Journal of Chemistry 13
all the methods Ru-C Ru-N and Ru-O vibrations are withinthe range of 500 to 720 which is far higher than the rangeof vibrations of Ru-Cl Ru-P and Ru-S which are foundwithin the range of 224 to 658 Generally the order of Ru-L vibrations can be assumed as Ru-N gt Ru-O gt Ru-C gtRu-Cl gt Ru-S gt Ru-P (Table 11) The wavenumbers of thevibrations computed from the different methods appear to besignificantly different from each other in values and positions(Figure 3) The features of the IR spectra using MP2 andCCSD are very similar in the models Some vibration around291506 in model Ru-O 303651 in Ru-Cl and 238544 inRu-S are very prominent in MP2 methods compared to inany other methods or even absent in other methods Forinstance the bending of the angle of HRuS which is found tobe prominent in MP2 method is completely absent in othermethods (see Figure 3 and Table 12) The MP2 and CCSDshow strong vibrations within the range of 3800 to 4100 inmany of the models which are obviously absent in manyof the PBE and B3LYP methods Using the PED methodas implemented in VEDA package most of these vibrationsat high frequencies are a result of the torsional and out-of-plane vibration of H-Ru-X-H where X represents the typeof the model as shown in Table 12 In addition most of thebending vibrations which are determined by PBE and B3LYPfrom 2800 to 3800 in the models are also determined byMP2 and CCSD though some cases are at lower wavenumbercompared to PBE and B3LYP (Table 12) In the models Ru-Oand Ru-Cl PBE and B3LYP give priority to the OH and RuHvibrations respectively whileMP2 andCCSD give priority tothe torsional stretching and angle bending of their atoms
4 Conclusions
Six models of Ru-L bonds Ru-C Ru-N Ru-O Ru-Cl Ru-P and Ru-S are built to represent common rutheniumcomplexes and possible ruthenium-receptor interactionsThe reproducibility of their geometrical electronic spec-troscopic and conductive properties was investigated usingMP2 CCSD PBE and B3LYP functionals with differentcombination of basis sets Generally we observed that thereproducibility of most of the properties is much easier usingdifferent basis sets compared to using different functionalmethods as a result of significant geometrical changes whichis possible especially if there are many light atoms likehydrogen atoms as in themodelsThe order of the energy andthe thermodynamic properties are found to be reproducibleusing different functionalmethods and basis sets butHOMOLUMO 119869-coupling hyperpolarizabilities and isotropic andanisotropic shielding are found to depend more on the typeof the functional used rather than on the type of the basis setThe only significant similarity observed among the methodsapplied in computing hyperpolarizabilities is that they allrated models Ru-S Ru-Cl and Ru-O among their best threeThe optimized geometries and the thermodynamic proper-ties obtained from the functional PBE are found to be verysimilar to MP2 and perform better than B3LYP and CCSDwhich further give insight into many literaturesrsquo preferencefor PBE in optimizing metal complexes In computation ofthe isotropic and anisotropic shielding tensors B3LYP gives
values similar to MP2 and performs better than PBE The IRvibrations and assignment clearly show that the vibrationsobtained from the MP2 and CCSD methods are very similarand give preference to the torsional and bending vibrationsof the molecules over their stretching The order of the IRvibrations of the ruthenium-ligand bonds can be assumed asRu-N gt Ru-O gt Ru-C gt Ru-Cl gt Ru-S gt Ru-P
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
The authors gracefully acknowledged the financial support ofGovan Mbeki Research and Development Centre Universityof Fort Hare South Africa The CHPC in Republic ofSouth Africa is gracefully acknowledged for providing thecomputing facilities and some of the software used for thecomputation
References
[1] B Dutta R Scopelliti and K Severin ldquoSynthesis structure andreactivity of the methoxy-bridged dimer [CpandRu(120583-OMe)]
2
(Cpand = 1205785-1-methoxy-24-di-tert-butyl-3-neopentylcyclopenta-dienyl)rdquo Organometallics vol 27 no 3 pp 423ndash429 2008
[2] M A Furrer F Schmitt M Wiederkehr L Juillerat-Jeanneretand B Therrien ldquoCellular delivery of pyrenyl-arene rutheniumcomplexes by a water-soluble arene ruthenium metalla-cagerdquoDalton Transactions vol 41 no 24 pp 7201ndash7211 2012
[3] Q ZhouW Lei YChen et al ldquoRuthenium(II)-arene complexeswith strong fluorescence insight into the underlying mecha-nismrdquoChemistrymdashA European Journal vol 18 no 28 pp 8617ndash8621 2012
[4] L Bıro E Farkas and P Buglyo ldquoHydrolytic behaviour andchloride ion binding capability of [Ru(1205786 minus119901minus cym)(H
2O)3]2+
a solution equilibrium studyrdquoDalton Transactions vol 41 no 1pp 285ndash291 2012
[5] Y Boutadla D L Davies R C Jones and K Singh ldquoThescope of ambiphilic acetate-assisted cyclometallation with half-sandwich complexes of iridium rhodium and rutheniumrdquoChemistrymdashA European Journal vol 17 no 12 pp 3438ndash34482011
[6] Y F Han H Li Y Fei Y J Lin W Z Zhang and GX Jin ldquoSynthesis and structural characterization of binuclearhalf-sandwich iridium rhodium and ruthenium complexescontaining 441015840-dipyridyldisulfide (4DPDS) ligandsrdquo DaltonTransactions vol 39 no 30 pp 7119ndash7124 2010
[7] B Dutta B F Curchod P Campomanes et al ldquoReactions ofalkynes with [RuCl(cyclopentadienyl)] complexes the impor-tant first stepsrdquo ChemistrymdashA European Journal vol 16 no 28pp 8400ndash8409 2010
[8] M Jimenez-Tenorio M C Puerta P Valerga S MonchoG Ujaque and A Lledos ldquoProton-transfer reactions to half-sandwich ruthenium trihydride complexes bearing hemilabilePN ligands experimental and density functional theory stud-iesrdquo Inorganic Chemistry vol 49 no 13 pp 6035ndash6057 2010
14 Journal of Chemistry
[9] B Dutta C Scolaro R Scopelliti P J Dyson and K Sev-erin ldquoImportance of the 120587-ligand remarkable effect of thecyclopentadienyl ring on the cytotoxicity of ruthenium PTAcompoundsrdquoOrganometallics vol 27 no 7 pp 1355ndash1357 2008
[10] T Bugarcic A Habtemariam J Stepankova et al ldquoThe con-trasting chemistry and cancer cell cytotoxicity of bipyridineand bipyridinediol ruthenium(II) arene complexesrdquo InorganicChemistry vol 47 no 24 pp 11470ndash11486 2008
[11] M Castellano-Castillo H Kostrhunova V Marini et al ldquoBind-ing ofmismatch repair proteinMutS tomispairedDNA adductsof intercalating ruthenium(II) arene complexesrdquo Journal ofBiological Inorganic Chemistry vol 13 no 6 pp 993ndash999 2008
[12] S J Dougan A Habtemariam S E McHale S Parsons andP J Sadler ldquoCatalytic organometallic anticancer complexesrdquoProceedings of the National Academy of Sciences of the UnitedStates of America vol 105 no 33 pp 11628ndash11633 2008
[13] S J Dougan M Melchart A Habtemariam S Parsons and PJ Sadler ldquoPhenylazo-pyridine and phenylazo-pyrazole chloridoruthenium(II) arene complexes arene loss aquation and can-cer cell cytotoxicityrdquo Inorganic Chemistry vol 45 no 26 pp10882ndash10894 2006
[14] V Ritleng P Bertani M Pfeffer C Sirlin and J HirschingerldquoOptically active ortho-metalated half-sandwich rutheniumcomplexes solid-state NMR as a convenient tool to analyzemixtures of diastereomersrdquo Inorganic Chemistry vol 40 no 20pp 5117ndash5122 2001
[15] Y Sunada Y Hayashi H Kawaguchi and K TatsumildquoAlkynethiolato and alkyneselenolato rutheniumhalf-sandwichcomplexes Synthesis structures and reactions with (1205785ndashC5H5)2Zrrdquo Inorganic Chemistry vol 40 no 27 pp 7072ndash70782001
[16] K Yamanari R Ito S Yamamoto et al ldquoCyclic tetramerscomposed of rhodium(III) iridium(III) or ruthenium(II) half-sandwich and6-purinethionesrdquo Inorganic Chemistry vol 41 no25 pp 6824ndash6830 2002
[17] F Caruso M Rossi A Benson et al ldquoRuthenium-arenecomplexes of curcumin X-ray and density functional the-ory structure synthesis and spectroscopic characterizationin vitro antitumor activity and DNA docking studies of (p-cymene)Ru(curcuminato)chlorordquo Journal of Medicinal Chem-istry vol 55 no 3 pp 1072ndash1081 2012
[18] C Gossens I Tavernelli and U Rothlisberger ldquoBinding oforganometallic ruthenium(II) anticancer compounds to nucle-obases a computational studyrdquo Journal of Physical Chemistry Avol 113 no 43 pp 11888ndash11897 2009
[19] A M Pizarro A Habtemariam and P J Sadler ldquoActiva-tion mechanisms for organometallic anticancer complexesrdquoin Medicinal Organometallic Chemistry vol 32 of Topics inOrganometallic Chemistry pp 21ndash56 Springer Berlin Ger-many 2010
[20] I Turel and J Kljun ldquoInteractions of metal ions with DNAits constituents and derivatives which may be relevant foranticancer researchrdquoCurrent Topics inMedicinal Chemistry vol11 no 21 pp 2661ndash2687 2011
[21] G Gasser I Ott and N Metzler-Nolte ldquoOrganometallic anti-cancer compoundsrdquo Journal of Medicinal Chemistry vol 54 no1 pp 3ndash25 2011
[22] K J Kilpin S Crot T Riedel J A Kitchen and P JDyson ldquoRuthenium(II) and osmium(II) 123-triazolylideneorganometallics a preliminary investigation into the biologicalactivity of rsquoclickrsquo carbene complexesrdquo Dalton Transactions vol43 no 3 pp 1443ndash1448 2014
[23] A F A Peacock S Parsons and P J Sadler ldquoTuning thehydrolytic aqueous chemistry of osmium arene complexeswith NO-chelating ligands to achieve cancer cell cytotoxicityrdquoJournal of the American Chemical Society vol 129 no 11 pp3348ndash3357 2007
[24] A F A Peacock M Melchart R J Deeth A Habtemariam SParsons and P J Sadler ldquoOsmium(II) and ruthenium(II) arenemaltolato complexes rapid hydrolysis and nucleobase bindingrdquoChemistrymdashA European Journal vol 13 no 9 pp 2601ndash26132007
[25] F Pelletier V Comte A Massard et al ldquoDevelopment ofbimetallic titanoceneminusrutheniumminusarene complexes as anti-cancer agents relationships between structural and biologicalpropertiesrdquo Journal of Medicinal Chemistry vol 53 no 19 pp6923ndash6933 2010
[26] K J Kilpin and P J Dyson ldquoEnzyme inhibition by metalcomplexes concepts strategies and applicationsrdquo ChemicalScience vol 4 no 4 pp 1410ndash1419 2013
[27] G Gasser andNMetzler-Nolte ldquoThe potential of organometal-lic complexes in medicinal chemistryrdquo Current Opinion inChemical Biology vol 16 no 1-2 pp 84ndash91 2012
[28] I Turel J Kljun F Perdih et al ldquoFirst ruthenium organometal-lic complex of antibacterial agent ofloxacin Crystal structureand interactions with DNArdquo Inorganic Chemistry vol 49 no23 pp 10750ndash10752 2010
[29] C Adamo and V Barone ldquoToward reliable density functionalmethods without adjustable parameters the PBE0 modelrdquoJournal of Chemical Physics vol 110 no 13 pp 6158ndash6170 1999
[30] A D Becke ldquoDensity-functional thermochemistry IIIThe roleof exact exchangerdquoThe Journal of Chemical Physics vol 98 no7 article 5648 1993
[31] W J Stevens M Krauss H Basch and P G Jasien ldquoRelativisticcompact effective potentials and efficient shared-exponentbasis sets for the third- fourth- and fifth-row atomsrdquoCanadianJournal of Chemistry vol 70 no 2 pp 612ndash630 1992
[32] M J Frisch GW Trucks H B Schlegel et alOfficial Gaussian09 Literature Citation Gaussian Wallingford UK 2009
[33] D J Feller ldquoThe role of databases in support of computationalchemistry calculationsrdquo Journal of Computational Chemistryvol 17 no 13 pp 1571ndash1586 1996
[34] K L Schuchardt B T Didier T Elsethagen et al ldquoBasis setexchange a community database for computational sciencesrdquoJournal of Chemical Information andModeling vol 47 no 3 pp1045ndash1052 2007
[35] Y Liu C-G Liu S-L Sun G-C Yang and Y-Q QiuldquoRedox-switching second-order nonlinear optical responses ofNandNandN ruthenium complexesrdquo Computational and TheoreticalChemistry vol 979 pp 112ndash118 2012
[36] P S Liyanage R M de Silva and K M N de Silva ldquoNonlinearoptical (NLO) properties of novel organometallic complexeshigh accuracy density functional theory (DFT) calculationsrdquoJournal of Molecular Structure THEOCHEM vol 639 pp 195ndash201 2003
[37] MH Jamroz ldquoVibrational EnergyDistributionAnalysis VEDA4 ProgramrdquoWarsaw Poland 2004ndash2010 httpwwwsmmgpl
[38] M H Jamroz J C Dobrowolski and R Brzozowski ldquoVibra-tional modes of 26- 27- and 23-diisopropylnaphthalene ADFT studyrdquo Journal of Molecular Structure vol 787 no 1ndash3 pp172ndash183 2006
[39] M H Jamroz ldquoVibrational Energy Distribution Analysis(VEDA) scopes and limitationsrdquo Spectrochimica Acta AMolec-ular and Biomolecular Spectroscopy vol 114 pp 220ndash230 2013
Journal of Chemistry 15
[40] R Marchal P Carbonniere D Begue and C Pouchan ldquoStruc-tural and vibrational determination of small galliumndasharsenideclusters fromCCSD(T) andDFT calculationsrdquoChemical PhysicsLetters vol 453 no 1ndash3 pp 49ndash54 2008
[41] R Marchal P Carbonniere and C Pouchan ldquoStructural andvibrational properties prediction of Sn
119899Te119899clusters (n = 2ndash
8) using the GSAM approachrdquo Computational and TheoreticalChemistry vol 990 pp 100ndash105 2012
[42] T Helgaker M Jaszunski and M Pecul ldquoThe quantum-chemical calculation of NMR indirect spin-spin coupling con-stantsrdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 53 no 4 pp 249ndash268 2008
[43] F A Perras andD L Bryce ldquoTheoretical study of homonuclear Jcoupling between quadrupolar spins single-crystal DOR andJ-resolved NMRrdquo Journal of Magnetic Resonance vol 242 pp23ndash32 2014
[44] I D Burns A F Hill A J P White D J Williams and J DE T Wilton-Ely ldquoPolyazolyl chelate chemistry 61 bidentatecoordination of HB(pz)
3(pz = Pyrazol-1-yl) to ruthenium and
osmium crystal structure of [RuH(CO)(PPh3)2k2-HB(pz)
3]rdquo
Organometallics vol 17 no 8 pp 1552ndash1557 1998[45] M Al-Noaimi and M A AlDamen ldquoRuthenium complexes
incorporating azoimine and 120572-diamine based ligands synthe-sis crystal structure electrochemistry and DFT calculationrdquoInorganica Chimica Acta vol 387 pp 45ndash51 2012
[46] K Nakajima Y Ando H Mano and M Kojima ldquoPhotosub-stitution reactivity crystal structures and electrochemistry ofruthenium(II) (III) complexes containing tetradentate (O
2N2
S2N2 and P
2N2) Schiff base ligandsrdquo Inorganica Chimica Acta
vol 274 no 2 pp 184ndash191 1998[47] Z-L Lu K Eichele I Warad et al ldquoSupported organometal-
lic complexes XXXVIII [1] Bis(methoxyethyldimethlphos-phine)ruthenium(II) complexes as transfer hydrogenation cat-alystsrdquo Zeitschrift fur Anorganische und Allgemeine Chemie vol629 no 7-8 pp 1308ndash1315 2003
[48] R Gaur and L Mishra ldquoSynthesis and characterization ofRu(II)ndashDMSOndashClndashchalcone complexes DNA binding nucle-ase and topoisomerase II inhibitory activityrdquo Inorganic Chem-istry vol 51 no 5 pp 3059ndash3070 2012
[49] B Cebrian-Losantos E Reisner C R Kowol et al ldquoSynthesisand reactivity of the aquation product of the antitumor complextrans-[Ru IIICI
4(indazole)
2] minusrdquo Inorganic Chemistry vol 47 no
14 pp 6513ndash6523 2008[50] B T Rasley M Rapta and R J Kulawiec ldquoDiastereoselectivity
in enolate coordination in a new class of chiral rutheniumenolate complexesrdquo Organometallics vol 15 no 13 pp 2852ndash2854 1996
[51] S David R S Perkins F R Fronczek S Kasiri S S MandalandR S Srivastava ldquoSynthesis characterization and anticanceractivity of ruthenium-pyrazole complexesrdquo Journal of InorganicBiochemistry vol 111 pp 33ndash39 2012
[52] B Dutta E Solari S Gauthier R Scopelliti and K SeverinldquoRuthenium half-sandwich complexes with sterically demand-ing cyclopentadienyl ligandsrdquo Organometallics vol 26 no 19pp 4791ndash4799 2007
[53] G Turkoglu S Tampier F Strinitz F W Heinemann E Hub-ner and N Burzlaff ldquoRuthenium carbonyl complexes bearingbis(pyrazol-1-yl)carboxylato ligandsrdquo Organometallics vol 31no 6 pp 2166ndash2174 2012
[54] A K Renfrew A D Phillips E Tapavicza R ScopellitiU Rothlisberger and P J Dyson ldquoTuning the efficacy of
ruthenium(II)-arene (RAPTA) antitumor compounds with flu-orinated arene ligandsrdquo Organometallics vol 28 no 17 pp5061ndash5071 2009
[55] P M Jeffries R E Ellenwood and G S Girolami ldquoAnionicruthenium(II) alkyls with ancillary diene and dienyl ligandssynthesis and structures of [(12057821205782-C
7H8)RuMe
4]2minus and [(12057831205782-
C8H11)RuMe
3]2minusrdquo Inorganica Chimica Acta vol 361 no 1 pp
3165ndash3170 2008[56] B R James D Dolphin T W Leung F W B Einstein
and A C Willis ldquoPreparation and characterization of someruthenium(III) porphyrins including the crystal structure ofbromo(octaethylporphinato)(triphenylphosphine)ruthenium(III)rdquoCanadian Journal of Chemistry vol 62 no 7 pp 1238ndash12451984
[57] M Plois R Wolf W Hujo and S Grimme ldquoTowards reagentsfor bimetallic activation reactions polyhydride complexes withRu2H3 Ru2ZnH6 and Cu
2Ru2H6coresrdquo European Journal of
Inorganic Chemistry vol 2013 no 17 pp 3039ndash3048 2013[58] L Hintermann L Xiao A Labonne and U Englert
ldquo[CpRu(1205786-naphthalene)]PF6as precursor in complex synthesis
and catalysis with the cyclopentadienyl-ruthenium(II) cationrdquoOrganometallics vol 28 no 19 pp 5739ndash5748 2009
[59] I W Wyman K N Robertson T S Cameron J C SwartsandM A S Aquino ldquoSynthesis structure and electrochemistryof (ferrocene-2-propenoato-OO1015840)bis[12-bis(diphenylphosphi-no)ethane-PP1015840]ruthenium(II) hexafluorophosphaterdquo Inorgan-ica Chimica Acta vol 359 no 9 pp 3092ndash3096 2006
[60] C A Vock C Scolaro A D Phillips R Scopelliti G Sava andP J Dyson ldquoSynthesis characterization and in vitro evaluationof novel ruthenium(II) 1205786-arene imidazole complexesrdquo Journalof Medicinal Chemistry vol 49 no 18 pp 5552ndash5561 2006
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
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Carbohydrate Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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CatalystsJournal of
Journal of Chemistry 5
Table 5The energy shielding tensors and 119869-coupling values usingMP2acc method and the differences using other computational methods(the energy values in Hartree)
Energy HOMO LUMO Ru-Iso Ru-Aniso X-Iso X-AnisoRu-C-MP2-acc minus440352 minus092 minus042 minus742180 1069111 minus14988 52269
Ru-N-MP2-acc minus441877 minus090 minus046 minus1176015 946597 minus82579 178860
Ru-O-MP2-acc minus443924 minus068 minus018 minus918858 846675 minus16694 119428
Ru-Cl-MP2-acc minus482319 minus062 minus020 minus1122411 1052228 29822 238476
Ru-P-MP2-acc minus470544 minus087 minus037 minus1359081 1488590 44861 4141
Ru-S-MP2-acc minus476385 minus061 minus016 minus313338 582699 minus80439 237577
000Ru-C-MP2-dv minus7849 000 000 26183 minus38901 1148 659
Ru-N-MP2-dv minus7926 000 minus001 71088 minus70110 3343 minus1344
Ru-O-MP2-dv minus7914 000 000 minus44694 minus39512 minus13768 24327
Ru-Cl-MP2-dv minus7924 000 000 minus37254 114475 minus19716 35479
Ru-P-MP2-dv minus7957 000 000 minus177917 246557 2518 minus037
Ru-S-MP2-dv minus7719 002 minus002 minus611650 135558 minus20580 35851
Ru-C-MP2-ECP 426878 000 minus001 596528 minus920085 1311 193
Ru-N-MP2- ECP 426800 000 000 960319 minus813149 7435 minus7455
Ru-O-MP2- ECP 426812 000 000 740324 minus715956 minus8299 15674
Ru-Cl-MP2- ECP 426802 000 000 914427 minus867435 minus16484 41130
Ru-P-MP2- ECP 426770 000 minus001 1093680 minus1218157 3260 minus1317
Ru-S-MP2- ECP 427007 003 minus003 149743 minus496580 13797 minus14494
Ru-C-PBE-dv minus8075 020 minus022 minus5106 minus767006 34929 minus46155
Ru-N-PBE-dv minus8156 018 minus020 629261 minus496409 52642 minus92641
Ru-O-PBE-dv minus8147 022 minus018 13816439 15984243 minus383942 413974
Ru-Cl-PBE-dv minus8176 015 minus018 10321955 13287550 minus491003 4370795
Ru-P-PBE-dv minus8201 021 minus021 16547451 37324221 374088 1446238
Ru-S-PBE-dv minus7973 018 minus019 10654331 10347455 minus659068 1230739
Ru-C-PBE-ECP 426764 021 minus021 663760 minus1027535 7597 minus17075
Ru-N-PBE-ECP 426681 018 minus020 1071404 minus884998 53035 minus93320
Ru-O-PBE-ECP 426690 022 minus018 minus3381033 38277943 minus3091812 35041247
Ru-Cl-PBE-ECP 426660 015 minus018 minus757542 2579402 27160896
Ru-P-PBE-ECP 426635 021 minus021 19109900 96261433
Ru-S-PBE-ECP 426863 018 minus019 9522596 32119344 11565209 35835334
Ru-C-B3LYP-dv minus8128 016 minus018 81227 minus588737 4860 minus12006
Ru-N-B3LYP-dv minus8211 013 minus017 431991 minus275591 45112 minus75540
Ru-O-B3LYP-dv minus8203 017 minus016 273324 minus381398 minus23391 6813
Ru-Cl-B3LYP-dv minus8246 012 minus016 254850 minus284675 minus265807 309548
Ru-P-B3LYP-dv minus8270 016 minus019 472561 minus646413 minus5451 9137
Ru-S-B3LYP-dv minus8041 014 minus017 minus225901 minus250444 30708 minus72243
Ru-C-B3LYP-ECP 426757 016 minus018 624966 minus1003953 4904 minus12301
Ru-N-B3LYP-ECP 426673 013 minus017 1040250 minus853188 45960 minus77145
Ru-O-B3LYP-ECP 426681 017 minus016 802053 minus780523 minus19773 minus244
Ru-Cl-B3LYP-ECP 426638 012 minus016 977624 minus948089 minus236464 264500
Ru-P-B3LYP-ECP 426614 016 minus018 1207902 minus1376028 minus4806 7968
Ru-S-B3LYP-ECP 426843 014 minus017 212424 minus536594 33276 minus74643
MP2-acc stands for MP2aug-cc-pVTZ MP2-dv stands for MP2DGDZVP MP2-ECP stands for MP2SBKJC VDZ PBE-dv stands for PBEDGDZVP PBE-ECP stands for PBESBKJC VDZ B3LYP-dv stands for B3LYPDGDZVP and B3LYP-ECP stands for B3LYPSBKJC VDZ
6 Journal of Chemistry
Table 6 Correlation of othermethods of computation with theMP2acc in computing energy HOMO LUMO and isotropic and anisotropicshielding
MP2DGDZVP MP2SBKJC VDZ PBEDGDZVP PBESBKJC VDZ B3LYPDGDZVP B3LYPSBKJC VDZEnergy 100 100 100 100 100 100
HOMO 100 100 099 099 099 099
LUMO 100 100 100 099 100 100
Ru-Iso 074 083 minus009 minus011 091 094
Ru-Aniso 095 097 051 050 084 082
X-Iso 098 098 067 minus051 minus016 minus012
X-Aniso 099 098 minus035 033 071 073
Table 7 119869-coupling of the Ru-L bonds at different level of computational methods
PBEDGDZVP PBESBKJC VDZ B3LYPDGDZVP B3LYPSBKJC VDZRu-C minus185119864 + 001 114119864 + 000 minus268119864 + 000 136119864 + 000
Ru-N minus146119864 + 001 753119864 minus 001 656119864 + 001 607119864 + 000
Ru-O 245119864 + 001 minus980119864 minus 001 249119864 + 001 minus117119864 + 000
Ru-Cl 472119864 + 001 563119864 + 000 476119864 + 001 590119864 + 000
Ru-P minus651119864 + 001 minus314119864 minus 001 minus714119864 + 001 minus500119864 minus 001
Ru-S minus752119864 minus 001 106119864 + 000 469119864 minus 001 135119864 + 000
Table 8 Correlation of 119869-coupling within the methods
PBEDGDZVP PBESBKJC VDZ B3LYPDGDZVP B3LYPSBKJC VDZPBE-dv 100 058 074 037PBE-ECP 058 100 042 073B3LYP-dv 074 042 100 072B3LYP-ECP 037 073 072 100
computational methods (Table 6) only the energy order isperfectly reproduced by all the methods There is a veryhigh similarity in the order of HOMO and LUMO especiallyLUMO computed using B3LYP In addition B3LYP is foundto also perform better in reproducing the shielding tensors ofRu and other atoms compared to PBE except for the orderof the isotropic shielding of other atoms besides Ru atomThe correlation obtained fromB3LYP in computing shieldingtensors further supports its reported better performance forthese properties [42]
In computation of the 119869-coupling we are only limited toB3LYP and PBE since these properties are not permitted inGaussian package at MP2 and CCSD level of theories Con-sidering the magnitude of 119869-coupling at B3LYPDGDZVP itfollows the order Ru-P gt Ru-N gt Ru-Cl gt Ru-S gt Ru-O gtRu-C (Table 7) The order is well reproduced in B3LYP withECP basis set but is poor in PBE and is even the worst whenPBE is combined with ECP basis set (Table 8) The simplereason for the variations is in support of the literature reportdemonstrating that the 119869-coupling is sensitive to bondinginteractions [43]
33 Hyperpolarizability Properties The values of the com-puted hyperpolarizabilities of the six models using differentfunctionals and basis sets are shown in Table 9 The values ofthe hyperpolarizabilities of themodels usingMP2 functionalsat different basis sets are in the order of Ru-S gt Ru-O gt Ru-Cl gt Ru-N gt Ru-P gt Ru-C which suggest the level of theirpossible modelling for NLO application The order obtained
from CCSD is Ru-O gt Ru-Cl gt Ru-S gt Ru-P gt Ru-N gt Ru-C the PBE methods give the order Ru-Cl gt Ru-C lt Ru-S gtRu-O gt Ru-P gt Ru-N and B3LYP gives the order Ru-Cl gtRu-O gt Ru-S gt Ru-P gt Ru-N gt Ru-C The MP2 rated Ru-S as the best model for NLO application while CCSD ratedmodel Ru-O as the best Also a different model Ru-Cl isindicated to have the highest hyperpolarizabilities using thefunctionals PBE and B3LYP irrespective of the basis set usedThe correlations of the hyperpolarizabilities values among themodels are shown in Table 10 The correlation table showsthat the order of the hyperpolarizabilities of the models isperfectly reproducible using the same MP2 at different basissets and also within CCSD at different basis sets Also B3LYPperforms better in reproducing its order at different basisset compared to PBE This clearly shows that the order ofthe hyperpolarizabilities depends greatly on the geometricalconfiguration and the type of the functional used rather thanon the type of the basis sets The only observed similarity inthe order of the hyperpolarizabilities computed with differentmethods is that all the methods rated the models Ru-S Ru-Cl and Ru-O among the best three except for PBE whichexcluded Ru-O from its best three
34 The IR Vibrations The IR vibrations of the modelsat different computational methods are shown in Figure 3The vibrations which are of significant interest to us aretheir Ru-ligand bonds of Ru-C Ru-N Ru-O Ru-Cl Ru-Pand Ru-S which are shown in Table 11 Also most of theprominent vibrations are assigned as shown in Table 12 In
Journal of Chemistry 7
Table9Th
efirsth
yperpo
lariz
ability(szlig)inesu(1times10minus30)v
aluesa
tdifferentcom
putatio
nalm
etho
ds
MP2
aug-cc-pV
TZMP2
DGDZV
PMP2
SBK
JCVDZ
CCSD
DGDZV
PCC
SDSBK
JCVDZ
PBEDGDZV
PPB
ESB
KJCVDZ
B3LY
PDGDZV
PB3
LYPSB
KJCVDZ
Ru-C
153
179
171
108
098
244
028
055
055
Ru-N
569
224
380
105
109
077
063
076
062
Ru-O
3505
1791
1860
822
548
178
160
220
205
Ru-C
l1173
1440
1325
558
547
284
289
325
313
Ru-P
177
180
213
124
151
152
147
135
137
Ru-S
28214
33591
11477
8295
315
214
182
207
165
8 Journal of Chemistry
Table10Th
ecorrelationwith
inthed
ifferentm
etho
dsused
incompu
tingthefi
rsth
yperpo
lariz
abilitie
s
MP2
aug-cc-pV
TZMP2
DGDZV
PMP2
SBK
JCVDZ
CCSD
DGDZV
PCC
SDSBK
JCVDZ
PBEDGDZV
PPB
ESB
KJCVDZ
B3LY
PDGDZV
PB3
LYPSB
KJCVDZ
MP2
-acc
100
100
100
004
014
019
030
024
010
MP2
-dv
100
100
100
minus001
010
020
029
022
009
MP2
-ecp
100
100
100
minus005
006
019
027
019
006
CCSD
-dv
004
minus001
minus005
100
095
031
062
075
075
CCSD
-ECP
014
010
006
095
100
045
081
092
091
PBE-dv
019
020
019
031
045
100
042
051
053
PBE-EC
P030
029
027
062
081
042
100
097
095
B3LY
P-dv
024
022
019
075
092
051
097
100
099
B3LY
P-EC
P010
009
006
075
091
053
095
099
100
Journal of Chemistry 9
200 300 400 500 600 700200 300 400 500 600 700
200 300 400 500 600 700200 300 400 500 600 700
200 300 400 500 600 700200 300 400 500 600 700
Ru-C-MP2Ru-C-CCSD
Ru-C-PBE0Ru-C-B3LYP
Ru-N-MP2Ru-N-CCSD
Ru-N-PBE0Ru-N-B3LYP
Ru-O-MP2Ru-O-CCSD
Ru-O-PBE0Ru-O-B3LYP
Ru-Cl-MP2Ru-Cl-CCSD
Ru-Cl-PBE0Ru-Cl-B3LYP
Ru-P-MP2Ru-P-CCSD
Ru-P-PBE0Ru-P-B3LYP
Ru-S-MP2Ru-S-CCSD
Ru-S-PBE0Ru-S-B3LYP
Figure 3 The IR vibrations of the six models computed using MP2 (black) CCSD (red) PBE (green) and B3LYP (blue)
10 Journal of Chemistry
Table11Th
eIRvibrations
oftheR
u-Lbo
ndsa
tdifferentcom
putatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
6077
72349120573(H
RuH)120592(Ru-C)
5872
73346120592(Ru-C)
68224
195
120592(Ru-C)
63297
226
120573(H
RuH)120592(Ru-C)
50222
238
120591(H
RuCH
)120592(Ru-C)
53062
71120573(H
RuH)120592(Ru-C)
Ru-N
71899
977
120592(Ru-N)120592(Ru-H)
62352
1636120592(Ru-N)
66265
2879120573(H
RuH)120592(Ru-N)
71495
1013
120592(Ru-N)
48235
101120592(Ru-N)
49539
738
120592(Ru-N)
65608
137
120573(H
RuH)120592(Ru-N)
Ru-O
7178
11371
120592(Ru-O)
63412
1586120592(Ru-O)
70574
75120592(Ru-O)
68889
2395
120592(Ru-O)
Ru-C
l43529
2195
120592(Ru-Cl)
5913
3644
120592(Ru-Cl)
65732
376
120592(Ru-Cl)
32331
1022
120592(Ru-Cl)
4478
43433
120592(Ru-Cl)
Ru-P
28203
171
120592(Ru-P)
2393
9395
120592(Ru-P)
44535
232
120592(Ru-P)
2793
71025
o(Ru
HPH
)120592(Ru-P)
23442
711
o(Ru
HPH
)120592(Ru-P)
Ru-S
4119
4401
120592(Ru-S)
32619
424
120592(Ru-S)
3574
92496
o(Ru
HSH
)120592(Ru-S)
40866
311
120592(Ru-S)
37311
597
o(Ru
HSH
)120592(Ru-S)
38596
1999
120592(Ru-S)
120592isstr
etching120573isbend
ing120591istorsionalandoisou
t-of-p
lane
torsional
Journal of Chemistry 11
Table12Th
eassignm
ento
fthe
prom
inentIRvibrations
ofthem
odels
atdifferent
compu
tatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
346783
9624120573(H
RuH)120592(Ru-H)
386628
124120573(H
RuH)120573(H
RuH)
120592(C
H)120592(Ru-H)
381759
1510
1120573(H
RuH)120573(H
RuH)
120591(H
RuHC)
30511
103120592(C
H)o(Ru
HCH
)120592(C
H)
313241
8772
120592(C
H)120592(C
H)
344585
6003
120592(Ru-H)
326534
582120573(H
CH)120592(C
H)120592(Ru-H)
3044
61
5191120592(C
H)o(Ru
HCH
)120592(Ru-H)
306501
5614120573(H
RuH)120573(H
RuH)
o(Ru
HCH
)323718
7402120573(H
CH)120573(H
RuH)120592(C
H)
310576
7913
120573(H
RuH)120592(Ru-H)
29104116677
120592(C
H)120592(C
H)
299873
14381
120592(C
H)120592(C
H)
310607
10481120573(H
RuC)
120591(H
CRuH
)o(Ru
HCH
)230969
6851120573(H
RuH)120591(H
RuHC)
120592(Ru-H)
247128
4498120573(H
RuH)o(Ru
HCH
)120592(Ru-H)
240085
1095
1120592(C
H)
231944
1014
7120573(H
RuC)
o(RuH
CH)
207553
969120573(H
RuH)120573(H
RuH)
120592(Ru-H)120592(Ru-H)
232314
1296
8120592(C
H)
Ru-N
38020714205120573(H
RuH)120573(H
RuH)
120573(H
RuH)
401043
1231120573(H
RuH)120591(H
RuHN)
120592(N
H)
403478
11428120591(H
RuNH)o(Ru
HNH)
120592(N
H)
353289
10673120573(H
RuH)120573(H
RuH)
339019
20019
120592(N
H)120592(N
H)
347897
18119120573(H
RuH)120573(H
RuH)
120591(H
RuHN)120592(Ru-H)
347497
1866120573(H
RuH)120573(H
RuH)
120592(Ru-H)
331504
19282
120592(N
H)120592(N
H)
32687139839
120592(N
H)120592(N
H)
336728
2897
5120592(Ru-H)
332695
1499
5120573(H
RuH)o(Ru
HNH)
318372
37524
120592(N
H)120592(N
H)
293151
4214120592(Ru-H)120592(Ru-H)120592(N
H)
120592(N
H)
327085
3514120573(H
RuH)120591(H
RuHN)
120592(Ru-H)
2746
17455
o(Ru
HNH)120592(Ru-H)
120592(Ru-H)
238961
4007120573(H
RuH)120592(Ru-H)
207916
6108
120592(Ru-H)
199979
4338
120573(H
NH)
210524
6443
o(Ru
HNH)120592(N
H)
120592(Ru-H)
203734
6557
120592(Ru-H)
Ru-O
372613
2694
9120592(O
H)
380749
28041
o(Ru
HOH)120592(Ru-H)
389061
1005
o(Ru
HOH)120573(H
RuH)
3608772399
3120592(O
H)
275932
1407120573(H
RuH)o(Ru
HOH)
o(Ru
HOH)120592(Ru-H)
31079
1921120573(H
RuO)120573(H
RuH)
o(Ru
HOH)
370979
51891120573(H
RuO)120573(H
RuO)
327956
2992120573(H
RuH)120573(H
RuH)
18598
2333
120592(Ru-H)120592(Ru-H)
179443
2374120573(H
RuH)o(Ru
HOH)
120592(Ru-H)
291506
5502
o(Ru
HOH)120592(Ru-H)
120592(Ru-H)
220079
1599120573(H
RuH)o(Ru
HOH)
120592(Ru-H)120592(Ru-H)
1346
08
2894120592(Ru-H)120592(Ru-H)
125632
2895120592(Ru-H)120573(H
ORu
)260461
4569120592(O
H)120573(H
ORu
)203014
1588
120592(Ru-H)
112741
9479120573(H
RuH)120592(Ru-H)
120592(Ru-H)
109235
7374
120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
205106
3383120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
147934
29120592(Ru-H)120592(Ru-H)
Ru-C
l185546
2458
120592(Ru-H)
308667
1411120573(H
RuH)o(Ru
HClH)
120592(Ru-H)
30365123653
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
22088
2242
120592(Ru-H)
131751
3288
120592(Ru-H)
179947
2511
o(Ru
HClH)120592(Ru-H)
120592(Ru-H)
261179
3015
120592(Ru-H)120573(H
RuH)
210816
1124
120592(Ru-H)
114581
9421
120592(Ru-H)
121159
3269120573(H
RuH)120573(H
RuH)
120573(H
RuCl)
20399
3006120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
203112
1687
120592(Ru-H)
84759
3157
120592(Ru-H)
110861
7222
o(Ru
HClH)o(Ru
HClH)
120592(Ru-H)120573(H
RuCl)
131224
3565
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
147293
3151
120592(Ru-H)
79488
381
120573(H
RuH)
7687
2483120573(H
RuH)120592(Ru-H)
120592(Ru-H)120592(Ru-H)
109164
1501120592(Ru-H)120573(H
RuH)
11346
9195
3120573(H
RuH)
12 Journal of Chemistry
Table12C
ontin
ued
B3LY
PCC
SDMP2
PBE
Ru-P
384575
1547
120573(H
RuH)
40856716207120573(H
RuH)120591(H
RuPH
)o(Ru
HPH
)410148
11361120573(H
RuH)120573(H
RuH)
3509879645120573(H
RuH)120592(Ru-H)
296363
1457120573(H
RuH)120592(Ru-H)
328227
1508120573(H
RuH)120573(H
RuH)
120591(H
PRuH
)264975
4273
120573(H
RuP)120592(Ru-H)
246259
4871
120592(PH)120592(PH)
253628
4006
120592(PH)120592(PH)
261721
3138
120592(Ru-H)
262336
4752
120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
24307
5689
120592(PH)120592(PH)
250603
4624
120592(PH)120592(PH)
259379
3579
120573(H
RuP)
256933
4865120573(H
RuP)120573
(HRu
H)
238468
1306120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
245899
7096
120592(PH)120592(PH)
255419
4427120573(H
RuH)120591(H
PRuH
)120591(H
PRuH
)228633
8692
120573(H
RuH)120592(PH)
237354
92120592(PH)
Ru-S
265041
1308
120592(SH)
290793
378120573(H
RuH)120591(H
SRuH
)120592(Ru-H)120573(H
RuS)
417199
15487
o(Ru
HSH
)o(Ru
HSH
)120573(H
RuH)
34606
2384120573(H
RuH)120573(H
RuH)
120573(H
RuH)o(Ru
HSH
)
26342
1916
120573(H
RuH)120592(Ru-H)
188073
1685120573(H
RuH)120573(H
RuH)
120592(Ru-H)
28041
199265120573(H
RuS)120573
(HRu
H)
120573(H
RuH)120592(Ru-H)
258225
1254
120592(SH)
1913
1699
120592(Ru-H)
114853
2967120591(H
SRuH
)120592(SH)
120592(Ru-H)
2385442392374
120573(H
RuS)
21675
2604
120592(Ru-H)
121642
3386120592(Ru-H)120592(Ru-H)
109859
10132120573(H
RuH)120591(H
SRuH
)o(Ru
HSH
)120592(Ru-H)
225761
44894
120592(Ru-H)120573(H
RuH)
132047
3699120592(Ru-H)120592(Ru-H)
11086
11006120573(H
RuH)120592(Ru-H)
82534
331120591(H
SRuH
)120592(Ru-H)
120592(Ru-H)
210643
5205
120592(Ru-H)
8835
5098
o(Ru
HSH
)o(Ru
HSH
)120592(Ru-H)120592(Ru-H)
Journal of Chemistry 13
all the methods Ru-C Ru-N and Ru-O vibrations are withinthe range of 500 to 720 which is far higher than the rangeof vibrations of Ru-Cl Ru-P and Ru-S which are foundwithin the range of 224 to 658 Generally the order of Ru-L vibrations can be assumed as Ru-N gt Ru-O gt Ru-C gtRu-Cl gt Ru-S gt Ru-P (Table 11) The wavenumbers of thevibrations computed from the different methods appear to besignificantly different from each other in values and positions(Figure 3) The features of the IR spectra using MP2 andCCSD are very similar in the models Some vibration around291506 in model Ru-O 303651 in Ru-Cl and 238544 inRu-S are very prominent in MP2 methods compared to inany other methods or even absent in other methods Forinstance the bending of the angle of HRuS which is found tobe prominent in MP2 method is completely absent in othermethods (see Figure 3 and Table 12) The MP2 and CCSDshow strong vibrations within the range of 3800 to 4100 inmany of the models which are obviously absent in manyof the PBE and B3LYP methods Using the PED methodas implemented in VEDA package most of these vibrationsat high frequencies are a result of the torsional and out-of-plane vibration of H-Ru-X-H where X represents the typeof the model as shown in Table 12 In addition most of thebending vibrations which are determined by PBE and B3LYPfrom 2800 to 3800 in the models are also determined byMP2 and CCSD though some cases are at lower wavenumbercompared to PBE and B3LYP (Table 12) In the models Ru-Oand Ru-Cl PBE and B3LYP give priority to the OH and RuHvibrations respectively whileMP2 andCCSD give priority tothe torsional stretching and angle bending of their atoms
4 Conclusions
Six models of Ru-L bonds Ru-C Ru-N Ru-O Ru-Cl Ru-P and Ru-S are built to represent common rutheniumcomplexes and possible ruthenium-receptor interactionsThe reproducibility of their geometrical electronic spec-troscopic and conductive properties was investigated usingMP2 CCSD PBE and B3LYP functionals with differentcombination of basis sets Generally we observed that thereproducibility of most of the properties is much easier usingdifferent basis sets compared to using different functionalmethods as a result of significant geometrical changes whichis possible especially if there are many light atoms likehydrogen atoms as in themodelsThe order of the energy andthe thermodynamic properties are found to be reproducibleusing different functionalmethods and basis sets butHOMOLUMO 119869-coupling hyperpolarizabilities and isotropic andanisotropic shielding are found to depend more on the typeof the functional used rather than on the type of the basis setThe only significant similarity observed among the methodsapplied in computing hyperpolarizabilities is that they allrated models Ru-S Ru-Cl and Ru-O among their best threeThe optimized geometries and the thermodynamic proper-ties obtained from the functional PBE are found to be verysimilar to MP2 and perform better than B3LYP and CCSDwhich further give insight into many literaturesrsquo preferencefor PBE in optimizing metal complexes In computation ofthe isotropic and anisotropic shielding tensors B3LYP gives
values similar to MP2 and performs better than PBE The IRvibrations and assignment clearly show that the vibrationsobtained from the MP2 and CCSD methods are very similarand give preference to the torsional and bending vibrationsof the molecules over their stretching The order of the IRvibrations of the ruthenium-ligand bonds can be assumed asRu-N gt Ru-O gt Ru-C gt Ru-Cl gt Ru-S gt Ru-P
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
The authors gracefully acknowledged the financial support ofGovan Mbeki Research and Development Centre Universityof Fort Hare South Africa The CHPC in Republic ofSouth Africa is gracefully acknowledged for providing thecomputing facilities and some of the software used for thecomputation
References
[1] B Dutta R Scopelliti and K Severin ldquoSynthesis structure andreactivity of the methoxy-bridged dimer [CpandRu(120583-OMe)]
2
(Cpand = 1205785-1-methoxy-24-di-tert-butyl-3-neopentylcyclopenta-dienyl)rdquo Organometallics vol 27 no 3 pp 423ndash429 2008
[2] M A Furrer F Schmitt M Wiederkehr L Juillerat-Jeanneretand B Therrien ldquoCellular delivery of pyrenyl-arene rutheniumcomplexes by a water-soluble arene ruthenium metalla-cagerdquoDalton Transactions vol 41 no 24 pp 7201ndash7211 2012
[3] Q ZhouW Lei YChen et al ldquoRuthenium(II)-arene complexeswith strong fluorescence insight into the underlying mecha-nismrdquoChemistrymdashA European Journal vol 18 no 28 pp 8617ndash8621 2012
[4] L Bıro E Farkas and P Buglyo ldquoHydrolytic behaviour andchloride ion binding capability of [Ru(1205786 minus119901minus cym)(H
2O)3]2+
a solution equilibrium studyrdquoDalton Transactions vol 41 no 1pp 285ndash291 2012
[5] Y Boutadla D L Davies R C Jones and K Singh ldquoThescope of ambiphilic acetate-assisted cyclometallation with half-sandwich complexes of iridium rhodium and rutheniumrdquoChemistrymdashA European Journal vol 17 no 12 pp 3438ndash34482011
[6] Y F Han H Li Y Fei Y J Lin W Z Zhang and GX Jin ldquoSynthesis and structural characterization of binuclearhalf-sandwich iridium rhodium and ruthenium complexescontaining 441015840-dipyridyldisulfide (4DPDS) ligandsrdquo DaltonTransactions vol 39 no 30 pp 7119ndash7124 2010
[7] B Dutta B F Curchod P Campomanes et al ldquoReactions ofalkynes with [RuCl(cyclopentadienyl)] complexes the impor-tant first stepsrdquo ChemistrymdashA European Journal vol 16 no 28pp 8400ndash8409 2010
[8] M Jimenez-Tenorio M C Puerta P Valerga S MonchoG Ujaque and A Lledos ldquoProton-transfer reactions to half-sandwich ruthenium trihydride complexes bearing hemilabilePN ligands experimental and density functional theory stud-iesrdquo Inorganic Chemistry vol 49 no 13 pp 6035ndash6057 2010
14 Journal of Chemistry
[9] B Dutta C Scolaro R Scopelliti P J Dyson and K Sev-erin ldquoImportance of the 120587-ligand remarkable effect of thecyclopentadienyl ring on the cytotoxicity of ruthenium PTAcompoundsrdquoOrganometallics vol 27 no 7 pp 1355ndash1357 2008
[10] T Bugarcic A Habtemariam J Stepankova et al ldquoThe con-trasting chemistry and cancer cell cytotoxicity of bipyridineand bipyridinediol ruthenium(II) arene complexesrdquo InorganicChemistry vol 47 no 24 pp 11470ndash11486 2008
[11] M Castellano-Castillo H Kostrhunova V Marini et al ldquoBind-ing ofmismatch repair proteinMutS tomispairedDNA adductsof intercalating ruthenium(II) arene complexesrdquo Journal ofBiological Inorganic Chemistry vol 13 no 6 pp 993ndash999 2008
[12] S J Dougan A Habtemariam S E McHale S Parsons andP J Sadler ldquoCatalytic organometallic anticancer complexesrdquoProceedings of the National Academy of Sciences of the UnitedStates of America vol 105 no 33 pp 11628ndash11633 2008
[13] S J Dougan M Melchart A Habtemariam S Parsons and PJ Sadler ldquoPhenylazo-pyridine and phenylazo-pyrazole chloridoruthenium(II) arene complexes arene loss aquation and can-cer cell cytotoxicityrdquo Inorganic Chemistry vol 45 no 26 pp10882ndash10894 2006
[14] V Ritleng P Bertani M Pfeffer C Sirlin and J HirschingerldquoOptically active ortho-metalated half-sandwich rutheniumcomplexes solid-state NMR as a convenient tool to analyzemixtures of diastereomersrdquo Inorganic Chemistry vol 40 no 20pp 5117ndash5122 2001
[15] Y Sunada Y Hayashi H Kawaguchi and K TatsumildquoAlkynethiolato and alkyneselenolato rutheniumhalf-sandwichcomplexes Synthesis structures and reactions with (1205785ndashC5H5)2Zrrdquo Inorganic Chemistry vol 40 no 27 pp 7072ndash70782001
[16] K Yamanari R Ito S Yamamoto et al ldquoCyclic tetramerscomposed of rhodium(III) iridium(III) or ruthenium(II) half-sandwich and6-purinethionesrdquo Inorganic Chemistry vol 41 no25 pp 6824ndash6830 2002
[17] F Caruso M Rossi A Benson et al ldquoRuthenium-arenecomplexes of curcumin X-ray and density functional the-ory structure synthesis and spectroscopic characterizationin vitro antitumor activity and DNA docking studies of (p-cymene)Ru(curcuminato)chlorordquo Journal of Medicinal Chem-istry vol 55 no 3 pp 1072ndash1081 2012
[18] C Gossens I Tavernelli and U Rothlisberger ldquoBinding oforganometallic ruthenium(II) anticancer compounds to nucle-obases a computational studyrdquo Journal of Physical Chemistry Avol 113 no 43 pp 11888ndash11897 2009
[19] A M Pizarro A Habtemariam and P J Sadler ldquoActiva-tion mechanisms for organometallic anticancer complexesrdquoin Medicinal Organometallic Chemistry vol 32 of Topics inOrganometallic Chemistry pp 21ndash56 Springer Berlin Ger-many 2010
[20] I Turel and J Kljun ldquoInteractions of metal ions with DNAits constituents and derivatives which may be relevant foranticancer researchrdquoCurrent Topics inMedicinal Chemistry vol11 no 21 pp 2661ndash2687 2011
[21] G Gasser I Ott and N Metzler-Nolte ldquoOrganometallic anti-cancer compoundsrdquo Journal of Medicinal Chemistry vol 54 no1 pp 3ndash25 2011
[22] K J Kilpin S Crot T Riedel J A Kitchen and P JDyson ldquoRuthenium(II) and osmium(II) 123-triazolylideneorganometallics a preliminary investigation into the biologicalactivity of rsquoclickrsquo carbene complexesrdquo Dalton Transactions vol43 no 3 pp 1443ndash1448 2014
[23] A F A Peacock S Parsons and P J Sadler ldquoTuning thehydrolytic aqueous chemistry of osmium arene complexeswith NO-chelating ligands to achieve cancer cell cytotoxicityrdquoJournal of the American Chemical Society vol 129 no 11 pp3348ndash3357 2007
[24] A F A Peacock M Melchart R J Deeth A Habtemariam SParsons and P J Sadler ldquoOsmium(II) and ruthenium(II) arenemaltolato complexes rapid hydrolysis and nucleobase bindingrdquoChemistrymdashA European Journal vol 13 no 9 pp 2601ndash26132007
[25] F Pelletier V Comte A Massard et al ldquoDevelopment ofbimetallic titanoceneminusrutheniumminusarene complexes as anti-cancer agents relationships between structural and biologicalpropertiesrdquo Journal of Medicinal Chemistry vol 53 no 19 pp6923ndash6933 2010
[26] K J Kilpin and P J Dyson ldquoEnzyme inhibition by metalcomplexes concepts strategies and applicationsrdquo ChemicalScience vol 4 no 4 pp 1410ndash1419 2013
[27] G Gasser andNMetzler-Nolte ldquoThe potential of organometal-lic complexes in medicinal chemistryrdquo Current Opinion inChemical Biology vol 16 no 1-2 pp 84ndash91 2012
[28] I Turel J Kljun F Perdih et al ldquoFirst ruthenium organometal-lic complex of antibacterial agent ofloxacin Crystal structureand interactions with DNArdquo Inorganic Chemistry vol 49 no23 pp 10750ndash10752 2010
[29] C Adamo and V Barone ldquoToward reliable density functionalmethods without adjustable parameters the PBE0 modelrdquoJournal of Chemical Physics vol 110 no 13 pp 6158ndash6170 1999
[30] A D Becke ldquoDensity-functional thermochemistry IIIThe roleof exact exchangerdquoThe Journal of Chemical Physics vol 98 no7 article 5648 1993
[31] W J Stevens M Krauss H Basch and P G Jasien ldquoRelativisticcompact effective potentials and efficient shared-exponentbasis sets for the third- fourth- and fifth-row atomsrdquoCanadianJournal of Chemistry vol 70 no 2 pp 612ndash630 1992
[32] M J Frisch GW Trucks H B Schlegel et alOfficial Gaussian09 Literature Citation Gaussian Wallingford UK 2009
[33] D J Feller ldquoThe role of databases in support of computationalchemistry calculationsrdquo Journal of Computational Chemistryvol 17 no 13 pp 1571ndash1586 1996
[34] K L Schuchardt B T Didier T Elsethagen et al ldquoBasis setexchange a community database for computational sciencesrdquoJournal of Chemical Information andModeling vol 47 no 3 pp1045ndash1052 2007
[35] Y Liu C-G Liu S-L Sun G-C Yang and Y-Q QiuldquoRedox-switching second-order nonlinear optical responses ofNandNandN ruthenium complexesrdquo Computational and TheoreticalChemistry vol 979 pp 112ndash118 2012
[36] P S Liyanage R M de Silva and K M N de Silva ldquoNonlinearoptical (NLO) properties of novel organometallic complexeshigh accuracy density functional theory (DFT) calculationsrdquoJournal of Molecular Structure THEOCHEM vol 639 pp 195ndash201 2003
[37] MH Jamroz ldquoVibrational EnergyDistributionAnalysis VEDA4 ProgramrdquoWarsaw Poland 2004ndash2010 httpwwwsmmgpl
[38] M H Jamroz J C Dobrowolski and R Brzozowski ldquoVibra-tional modes of 26- 27- and 23-diisopropylnaphthalene ADFT studyrdquo Journal of Molecular Structure vol 787 no 1ndash3 pp172ndash183 2006
[39] M H Jamroz ldquoVibrational Energy Distribution Analysis(VEDA) scopes and limitationsrdquo Spectrochimica Acta AMolec-ular and Biomolecular Spectroscopy vol 114 pp 220ndash230 2013
Journal of Chemistry 15
[40] R Marchal P Carbonniere D Begue and C Pouchan ldquoStruc-tural and vibrational determination of small galliumndasharsenideclusters fromCCSD(T) andDFT calculationsrdquoChemical PhysicsLetters vol 453 no 1ndash3 pp 49ndash54 2008
[41] R Marchal P Carbonniere and C Pouchan ldquoStructural andvibrational properties prediction of Sn
119899Te119899clusters (n = 2ndash
8) using the GSAM approachrdquo Computational and TheoreticalChemistry vol 990 pp 100ndash105 2012
[42] T Helgaker M Jaszunski and M Pecul ldquoThe quantum-chemical calculation of NMR indirect spin-spin coupling con-stantsrdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 53 no 4 pp 249ndash268 2008
[43] F A Perras andD L Bryce ldquoTheoretical study of homonuclear Jcoupling between quadrupolar spins single-crystal DOR andJ-resolved NMRrdquo Journal of Magnetic Resonance vol 242 pp23ndash32 2014
[44] I D Burns A F Hill A J P White D J Williams and J DE T Wilton-Ely ldquoPolyazolyl chelate chemistry 61 bidentatecoordination of HB(pz)
3(pz = Pyrazol-1-yl) to ruthenium and
osmium crystal structure of [RuH(CO)(PPh3)2k2-HB(pz)
3]rdquo
Organometallics vol 17 no 8 pp 1552ndash1557 1998[45] M Al-Noaimi and M A AlDamen ldquoRuthenium complexes
incorporating azoimine and 120572-diamine based ligands synthe-sis crystal structure electrochemistry and DFT calculationrdquoInorganica Chimica Acta vol 387 pp 45ndash51 2012
[46] K Nakajima Y Ando H Mano and M Kojima ldquoPhotosub-stitution reactivity crystal structures and electrochemistry ofruthenium(II) (III) complexes containing tetradentate (O
2N2
S2N2 and P
2N2) Schiff base ligandsrdquo Inorganica Chimica Acta
vol 274 no 2 pp 184ndash191 1998[47] Z-L Lu K Eichele I Warad et al ldquoSupported organometal-
lic complexes XXXVIII [1] Bis(methoxyethyldimethlphos-phine)ruthenium(II) complexes as transfer hydrogenation cat-alystsrdquo Zeitschrift fur Anorganische und Allgemeine Chemie vol629 no 7-8 pp 1308ndash1315 2003
[48] R Gaur and L Mishra ldquoSynthesis and characterization ofRu(II)ndashDMSOndashClndashchalcone complexes DNA binding nucle-ase and topoisomerase II inhibitory activityrdquo Inorganic Chem-istry vol 51 no 5 pp 3059ndash3070 2012
[49] B Cebrian-Losantos E Reisner C R Kowol et al ldquoSynthesisand reactivity of the aquation product of the antitumor complextrans-[Ru IIICI
4(indazole)
2] minusrdquo Inorganic Chemistry vol 47 no
14 pp 6513ndash6523 2008[50] B T Rasley M Rapta and R J Kulawiec ldquoDiastereoselectivity
in enolate coordination in a new class of chiral rutheniumenolate complexesrdquo Organometallics vol 15 no 13 pp 2852ndash2854 1996
[51] S David R S Perkins F R Fronczek S Kasiri S S MandalandR S Srivastava ldquoSynthesis characterization and anticanceractivity of ruthenium-pyrazole complexesrdquo Journal of InorganicBiochemistry vol 111 pp 33ndash39 2012
[52] B Dutta E Solari S Gauthier R Scopelliti and K SeverinldquoRuthenium half-sandwich complexes with sterically demand-ing cyclopentadienyl ligandsrdquo Organometallics vol 26 no 19pp 4791ndash4799 2007
[53] G Turkoglu S Tampier F Strinitz F W Heinemann E Hub-ner and N Burzlaff ldquoRuthenium carbonyl complexes bearingbis(pyrazol-1-yl)carboxylato ligandsrdquo Organometallics vol 31no 6 pp 2166ndash2174 2012
[54] A K Renfrew A D Phillips E Tapavicza R ScopellitiU Rothlisberger and P J Dyson ldquoTuning the efficacy of
ruthenium(II)-arene (RAPTA) antitumor compounds with flu-orinated arene ligandsrdquo Organometallics vol 28 no 17 pp5061ndash5071 2009
[55] P M Jeffries R E Ellenwood and G S Girolami ldquoAnionicruthenium(II) alkyls with ancillary diene and dienyl ligandssynthesis and structures of [(12057821205782-C
7H8)RuMe
4]2minus and [(12057831205782-
C8H11)RuMe
3]2minusrdquo Inorganica Chimica Acta vol 361 no 1 pp
3165ndash3170 2008[56] B R James D Dolphin T W Leung F W B Einstein
and A C Willis ldquoPreparation and characterization of someruthenium(III) porphyrins including the crystal structure ofbromo(octaethylporphinato)(triphenylphosphine)ruthenium(III)rdquoCanadian Journal of Chemistry vol 62 no 7 pp 1238ndash12451984
[57] M Plois R Wolf W Hujo and S Grimme ldquoTowards reagentsfor bimetallic activation reactions polyhydride complexes withRu2H3 Ru2ZnH6 and Cu
2Ru2H6coresrdquo European Journal of
Inorganic Chemistry vol 2013 no 17 pp 3039ndash3048 2013[58] L Hintermann L Xiao A Labonne and U Englert
ldquo[CpRu(1205786-naphthalene)]PF6as precursor in complex synthesis
and catalysis with the cyclopentadienyl-ruthenium(II) cationrdquoOrganometallics vol 28 no 19 pp 5739ndash5748 2009
[59] I W Wyman K N Robertson T S Cameron J C SwartsandM A S Aquino ldquoSynthesis structure and electrochemistryof (ferrocene-2-propenoato-OO1015840)bis[12-bis(diphenylphosphi-no)ethane-PP1015840]ruthenium(II) hexafluorophosphaterdquo Inorgan-ica Chimica Acta vol 359 no 9 pp 3092ndash3096 2006
[60] C A Vock C Scolaro A D Phillips R Scopelliti G Sava andP J Dyson ldquoSynthesis characterization and in vitro evaluationof novel ruthenium(II) 1205786-arene imidazole complexesrdquo Journalof Medicinal Chemistry vol 49 no 18 pp 5552ndash5561 2006
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
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Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
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Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
6 Journal of Chemistry
Table 6 Correlation of othermethods of computation with theMP2acc in computing energy HOMO LUMO and isotropic and anisotropicshielding
MP2DGDZVP MP2SBKJC VDZ PBEDGDZVP PBESBKJC VDZ B3LYPDGDZVP B3LYPSBKJC VDZEnergy 100 100 100 100 100 100
HOMO 100 100 099 099 099 099
LUMO 100 100 100 099 100 100
Ru-Iso 074 083 minus009 minus011 091 094
Ru-Aniso 095 097 051 050 084 082
X-Iso 098 098 067 minus051 minus016 minus012
X-Aniso 099 098 minus035 033 071 073
Table 7 119869-coupling of the Ru-L bonds at different level of computational methods
PBEDGDZVP PBESBKJC VDZ B3LYPDGDZVP B3LYPSBKJC VDZRu-C minus185119864 + 001 114119864 + 000 minus268119864 + 000 136119864 + 000
Ru-N minus146119864 + 001 753119864 minus 001 656119864 + 001 607119864 + 000
Ru-O 245119864 + 001 minus980119864 minus 001 249119864 + 001 minus117119864 + 000
Ru-Cl 472119864 + 001 563119864 + 000 476119864 + 001 590119864 + 000
Ru-P minus651119864 + 001 minus314119864 minus 001 minus714119864 + 001 minus500119864 minus 001
Ru-S minus752119864 minus 001 106119864 + 000 469119864 minus 001 135119864 + 000
Table 8 Correlation of 119869-coupling within the methods
PBEDGDZVP PBESBKJC VDZ B3LYPDGDZVP B3LYPSBKJC VDZPBE-dv 100 058 074 037PBE-ECP 058 100 042 073B3LYP-dv 074 042 100 072B3LYP-ECP 037 073 072 100
computational methods (Table 6) only the energy order isperfectly reproduced by all the methods There is a veryhigh similarity in the order of HOMO and LUMO especiallyLUMO computed using B3LYP In addition B3LYP is foundto also perform better in reproducing the shielding tensors ofRu and other atoms compared to PBE except for the orderof the isotropic shielding of other atoms besides Ru atomThe correlation obtained fromB3LYP in computing shieldingtensors further supports its reported better performance forthese properties [42]
In computation of the 119869-coupling we are only limited toB3LYP and PBE since these properties are not permitted inGaussian package at MP2 and CCSD level of theories Con-sidering the magnitude of 119869-coupling at B3LYPDGDZVP itfollows the order Ru-P gt Ru-N gt Ru-Cl gt Ru-S gt Ru-O gtRu-C (Table 7) The order is well reproduced in B3LYP withECP basis set but is poor in PBE and is even the worst whenPBE is combined with ECP basis set (Table 8) The simplereason for the variations is in support of the literature reportdemonstrating that the 119869-coupling is sensitive to bondinginteractions [43]
33 Hyperpolarizability Properties The values of the com-puted hyperpolarizabilities of the six models using differentfunctionals and basis sets are shown in Table 9 The values ofthe hyperpolarizabilities of themodels usingMP2 functionalsat different basis sets are in the order of Ru-S gt Ru-O gt Ru-Cl gt Ru-N gt Ru-P gt Ru-C which suggest the level of theirpossible modelling for NLO application The order obtained
from CCSD is Ru-O gt Ru-Cl gt Ru-S gt Ru-P gt Ru-N gt Ru-C the PBE methods give the order Ru-Cl gt Ru-C lt Ru-S gtRu-O gt Ru-P gt Ru-N and B3LYP gives the order Ru-Cl gtRu-O gt Ru-S gt Ru-P gt Ru-N gt Ru-C The MP2 rated Ru-S as the best model for NLO application while CCSD ratedmodel Ru-O as the best Also a different model Ru-Cl isindicated to have the highest hyperpolarizabilities using thefunctionals PBE and B3LYP irrespective of the basis set usedThe correlations of the hyperpolarizabilities values among themodels are shown in Table 10 The correlation table showsthat the order of the hyperpolarizabilities of the models isperfectly reproducible using the same MP2 at different basissets and also within CCSD at different basis sets Also B3LYPperforms better in reproducing its order at different basisset compared to PBE This clearly shows that the order ofthe hyperpolarizabilities depends greatly on the geometricalconfiguration and the type of the functional used rather thanon the type of the basis sets The only observed similarity inthe order of the hyperpolarizabilities computed with differentmethods is that all the methods rated the models Ru-S Ru-Cl and Ru-O among the best three except for PBE whichexcluded Ru-O from its best three
34 The IR Vibrations The IR vibrations of the modelsat different computational methods are shown in Figure 3The vibrations which are of significant interest to us aretheir Ru-ligand bonds of Ru-C Ru-N Ru-O Ru-Cl Ru-Pand Ru-S which are shown in Table 11 Also most of theprominent vibrations are assigned as shown in Table 12 In
Journal of Chemistry 7
Table9Th
efirsth
yperpo
lariz
ability(szlig)inesu(1times10minus30)v
aluesa
tdifferentcom
putatio
nalm
etho
ds
MP2
aug-cc-pV
TZMP2
DGDZV
PMP2
SBK
JCVDZ
CCSD
DGDZV
PCC
SDSBK
JCVDZ
PBEDGDZV
PPB
ESB
KJCVDZ
B3LY
PDGDZV
PB3
LYPSB
KJCVDZ
Ru-C
153
179
171
108
098
244
028
055
055
Ru-N
569
224
380
105
109
077
063
076
062
Ru-O
3505
1791
1860
822
548
178
160
220
205
Ru-C
l1173
1440
1325
558
547
284
289
325
313
Ru-P
177
180
213
124
151
152
147
135
137
Ru-S
28214
33591
11477
8295
315
214
182
207
165
8 Journal of Chemistry
Table10Th
ecorrelationwith
inthed
ifferentm
etho
dsused
incompu
tingthefi
rsth
yperpo
lariz
abilitie
s
MP2
aug-cc-pV
TZMP2
DGDZV
PMP2
SBK
JCVDZ
CCSD
DGDZV
PCC
SDSBK
JCVDZ
PBEDGDZV
PPB
ESB
KJCVDZ
B3LY
PDGDZV
PB3
LYPSB
KJCVDZ
MP2
-acc
100
100
100
004
014
019
030
024
010
MP2
-dv
100
100
100
minus001
010
020
029
022
009
MP2
-ecp
100
100
100
minus005
006
019
027
019
006
CCSD
-dv
004
minus001
minus005
100
095
031
062
075
075
CCSD
-ECP
014
010
006
095
100
045
081
092
091
PBE-dv
019
020
019
031
045
100
042
051
053
PBE-EC
P030
029
027
062
081
042
100
097
095
B3LY
P-dv
024
022
019
075
092
051
097
100
099
B3LY
P-EC
P010
009
006
075
091
053
095
099
100
Journal of Chemistry 9
200 300 400 500 600 700200 300 400 500 600 700
200 300 400 500 600 700200 300 400 500 600 700
200 300 400 500 600 700200 300 400 500 600 700
Ru-C-MP2Ru-C-CCSD
Ru-C-PBE0Ru-C-B3LYP
Ru-N-MP2Ru-N-CCSD
Ru-N-PBE0Ru-N-B3LYP
Ru-O-MP2Ru-O-CCSD
Ru-O-PBE0Ru-O-B3LYP
Ru-Cl-MP2Ru-Cl-CCSD
Ru-Cl-PBE0Ru-Cl-B3LYP
Ru-P-MP2Ru-P-CCSD
Ru-P-PBE0Ru-P-B3LYP
Ru-S-MP2Ru-S-CCSD
Ru-S-PBE0Ru-S-B3LYP
Figure 3 The IR vibrations of the six models computed using MP2 (black) CCSD (red) PBE (green) and B3LYP (blue)
10 Journal of Chemistry
Table11Th
eIRvibrations
oftheR
u-Lbo
ndsa
tdifferentcom
putatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
6077
72349120573(H
RuH)120592(Ru-C)
5872
73346120592(Ru-C)
68224
195
120592(Ru-C)
63297
226
120573(H
RuH)120592(Ru-C)
50222
238
120591(H
RuCH
)120592(Ru-C)
53062
71120573(H
RuH)120592(Ru-C)
Ru-N
71899
977
120592(Ru-N)120592(Ru-H)
62352
1636120592(Ru-N)
66265
2879120573(H
RuH)120592(Ru-N)
71495
1013
120592(Ru-N)
48235
101120592(Ru-N)
49539
738
120592(Ru-N)
65608
137
120573(H
RuH)120592(Ru-N)
Ru-O
7178
11371
120592(Ru-O)
63412
1586120592(Ru-O)
70574
75120592(Ru-O)
68889
2395
120592(Ru-O)
Ru-C
l43529
2195
120592(Ru-Cl)
5913
3644
120592(Ru-Cl)
65732
376
120592(Ru-Cl)
32331
1022
120592(Ru-Cl)
4478
43433
120592(Ru-Cl)
Ru-P
28203
171
120592(Ru-P)
2393
9395
120592(Ru-P)
44535
232
120592(Ru-P)
2793
71025
o(Ru
HPH
)120592(Ru-P)
23442
711
o(Ru
HPH
)120592(Ru-P)
Ru-S
4119
4401
120592(Ru-S)
32619
424
120592(Ru-S)
3574
92496
o(Ru
HSH
)120592(Ru-S)
40866
311
120592(Ru-S)
37311
597
o(Ru
HSH
)120592(Ru-S)
38596
1999
120592(Ru-S)
120592isstr
etching120573isbend
ing120591istorsionalandoisou
t-of-p
lane
torsional
Journal of Chemistry 11
Table12Th
eassignm
ento
fthe
prom
inentIRvibrations
ofthem
odels
atdifferent
compu
tatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
346783
9624120573(H
RuH)120592(Ru-H)
386628
124120573(H
RuH)120573(H
RuH)
120592(C
H)120592(Ru-H)
381759
1510
1120573(H
RuH)120573(H
RuH)
120591(H
RuHC)
30511
103120592(C
H)o(Ru
HCH
)120592(C
H)
313241
8772
120592(C
H)120592(C
H)
344585
6003
120592(Ru-H)
326534
582120573(H
CH)120592(C
H)120592(Ru-H)
3044
61
5191120592(C
H)o(Ru
HCH
)120592(Ru-H)
306501
5614120573(H
RuH)120573(H
RuH)
o(Ru
HCH
)323718
7402120573(H
CH)120573(H
RuH)120592(C
H)
310576
7913
120573(H
RuH)120592(Ru-H)
29104116677
120592(C
H)120592(C
H)
299873
14381
120592(C
H)120592(C
H)
310607
10481120573(H
RuC)
120591(H
CRuH
)o(Ru
HCH
)230969
6851120573(H
RuH)120591(H
RuHC)
120592(Ru-H)
247128
4498120573(H
RuH)o(Ru
HCH
)120592(Ru-H)
240085
1095
1120592(C
H)
231944
1014
7120573(H
RuC)
o(RuH
CH)
207553
969120573(H
RuH)120573(H
RuH)
120592(Ru-H)120592(Ru-H)
232314
1296
8120592(C
H)
Ru-N
38020714205120573(H
RuH)120573(H
RuH)
120573(H
RuH)
401043
1231120573(H
RuH)120591(H
RuHN)
120592(N
H)
403478
11428120591(H
RuNH)o(Ru
HNH)
120592(N
H)
353289
10673120573(H
RuH)120573(H
RuH)
339019
20019
120592(N
H)120592(N
H)
347897
18119120573(H
RuH)120573(H
RuH)
120591(H
RuHN)120592(Ru-H)
347497
1866120573(H
RuH)120573(H
RuH)
120592(Ru-H)
331504
19282
120592(N
H)120592(N
H)
32687139839
120592(N
H)120592(N
H)
336728
2897
5120592(Ru-H)
332695
1499
5120573(H
RuH)o(Ru
HNH)
318372
37524
120592(N
H)120592(N
H)
293151
4214120592(Ru-H)120592(Ru-H)120592(N
H)
120592(N
H)
327085
3514120573(H
RuH)120591(H
RuHN)
120592(Ru-H)
2746
17455
o(Ru
HNH)120592(Ru-H)
120592(Ru-H)
238961
4007120573(H
RuH)120592(Ru-H)
207916
6108
120592(Ru-H)
199979
4338
120573(H
NH)
210524
6443
o(Ru
HNH)120592(N
H)
120592(Ru-H)
203734
6557
120592(Ru-H)
Ru-O
372613
2694
9120592(O
H)
380749
28041
o(Ru
HOH)120592(Ru-H)
389061
1005
o(Ru
HOH)120573(H
RuH)
3608772399
3120592(O
H)
275932
1407120573(H
RuH)o(Ru
HOH)
o(Ru
HOH)120592(Ru-H)
31079
1921120573(H
RuO)120573(H
RuH)
o(Ru
HOH)
370979
51891120573(H
RuO)120573(H
RuO)
327956
2992120573(H
RuH)120573(H
RuH)
18598
2333
120592(Ru-H)120592(Ru-H)
179443
2374120573(H
RuH)o(Ru
HOH)
120592(Ru-H)
291506
5502
o(Ru
HOH)120592(Ru-H)
120592(Ru-H)
220079
1599120573(H
RuH)o(Ru
HOH)
120592(Ru-H)120592(Ru-H)
1346
08
2894120592(Ru-H)120592(Ru-H)
125632
2895120592(Ru-H)120573(H
ORu
)260461
4569120592(O
H)120573(H
ORu
)203014
1588
120592(Ru-H)
112741
9479120573(H
RuH)120592(Ru-H)
120592(Ru-H)
109235
7374
120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
205106
3383120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
147934
29120592(Ru-H)120592(Ru-H)
Ru-C
l185546
2458
120592(Ru-H)
308667
1411120573(H
RuH)o(Ru
HClH)
120592(Ru-H)
30365123653
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
22088
2242
120592(Ru-H)
131751
3288
120592(Ru-H)
179947
2511
o(Ru
HClH)120592(Ru-H)
120592(Ru-H)
261179
3015
120592(Ru-H)120573(H
RuH)
210816
1124
120592(Ru-H)
114581
9421
120592(Ru-H)
121159
3269120573(H
RuH)120573(H
RuH)
120573(H
RuCl)
20399
3006120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
203112
1687
120592(Ru-H)
84759
3157
120592(Ru-H)
110861
7222
o(Ru
HClH)o(Ru
HClH)
120592(Ru-H)120573(H
RuCl)
131224
3565
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
147293
3151
120592(Ru-H)
79488
381
120573(H
RuH)
7687
2483120573(H
RuH)120592(Ru-H)
120592(Ru-H)120592(Ru-H)
109164
1501120592(Ru-H)120573(H
RuH)
11346
9195
3120573(H
RuH)
12 Journal of Chemistry
Table12C
ontin
ued
B3LY
PCC
SDMP2
PBE
Ru-P
384575
1547
120573(H
RuH)
40856716207120573(H
RuH)120591(H
RuPH
)o(Ru
HPH
)410148
11361120573(H
RuH)120573(H
RuH)
3509879645120573(H
RuH)120592(Ru-H)
296363
1457120573(H
RuH)120592(Ru-H)
328227
1508120573(H
RuH)120573(H
RuH)
120591(H
PRuH
)264975
4273
120573(H
RuP)120592(Ru-H)
246259
4871
120592(PH)120592(PH)
253628
4006
120592(PH)120592(PH)
261721
3138
120592(Ru-H)
262336
4752
120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
24307
5689
120592(PH)120592(PH)
250603
4624
120592(PH)120592(PH)
259379
3579
120573(H
RuP)
256933
4865120573(H
RuP)120573
(HRu
H)
238468
1306120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
245899
7096
120592(PH)120592(PH)
255419
4427120573(H
RuH)120591(H
PRuH
)120591(H
PRuH
)228633
8692
120573(H
RuH)120592(PH)
237354
92120592(PH)
Ru-S
265041
1308
120592(SH)
290793
378120573(H
RuH)120591(H
SRuH
)120592(Ru-H)120573(H
RuS)
417199
15487
o(Ru
HSH
)o(Ru
HSH
)120573(H
RuH)
34606
2384120573(H
RuH)120573(H
RuH)
120573(H
RuH)o(Ru
HSH
)
26342
1916
120573(H
RuH)120592(Ru-H)
188073
1685120573(H
RuH)120573(H
RuH)
120592(Ru-H)
28041
199265120573(H
RuS)120573
(HRu
H)
120573(H
RuH)120592(Ru-H)
258225
1254
120592(SH)
1913
1699
120592(Ru-H)
114853
2967120591(H
SRuH
)120592(SH)
120592(Ru-H)
2385442392374
120573(H
RuS)
21675
2604
120592(Ru-H)
121642
3386120592(Ru-H)120592(Ru-H)
109859
10132120573(H
RuH)120591(H
SRuH
)o(Ru
HSH
)120592(Ru-H)
225761
44894
120592(Ru-H)120573(H
RuH)
132047
3699120592(Ru-H)120592(Ru-H)
11086
11006120573(H
RuH)120592(Ru-H)
82534
331120591(H
SRuH
)120592(Ru-H)
120592(Ru-H)
210643
5205
120592(Ru-H)
8835
5098
o(Ru
HSH
)o(Ru
HSH
)120592(Ru-H)120592(Ru-H)
Journal of Chemistry 13
all the methods Ru-C Ru-N and Ru-O vibrations are withinthe range of 500 to 720 which is far higher than the rangeof vibrations of Ru-Cl Ru-P and Ru-S which are foundwithin the range of 224 to 658 Generally the order of Ru-L vibrations can be assumed as Ru-N gt Ru-O gt Ru-C gtRu-Cl gt Ru-S gt Ru-P (Table 11) The wavenumbers of thevibrations computed from the different methods appear to besignificantly different from each other in values and positions(Figure 3) The features of the IR spectra using MP2 andCCSD are very similar in the models Some vibration around291506 in model Ru-O 303651 in Ru-Cl and 238544 inRu-S are very prominent in MP2 methods compared to inany other methods or even absent in other methods Forinstance the bending of the angle of HRuS which is found tobe prominent in MP2 method is completely absent in othermethods (see Figure 3 and Table 12) The MP2 and CCSDshow strong vibrations within the range of 3800 to 4100 inmany of the models which are obviously absent in manyof the PBE and B3LYP methods Using the PED methodas implemented in VEDA package most of these vibrationsat high frequencies are a result of the torsional and out-of-plane vibration of H-Ru-X-H where X represents the typeof the model as shown in Table 12 In addition most of thebending vibrations which are determined by PBE and B3LYPfrom 2800 to 3800 in the models are also determined byMP2 and CCSD though some cases are at lower wavenumbercompared to PBE and B3LYP (Table 12) In the models Ru-Oand Ru-Cl PBE and B3LYP give priority to the OH and RuHvibrations respectively whileMP2 andCCSD give priority tothe torsional stretching and angle bending of their atoms
4 Conclusions
Six models of Ru-L bonds Ru-C Ru-N Ru-O Ru-Cl Ru-P and Ru-S are built to represent common rutheniumcomplexes and possible ruthenium-receptor interactionsThe reproducibility of their geometrical electronic spec-troscopic and conductive properties was investigated usingMP2 CCSD PBE and B3LYP functionals with differentcombination of basis sets Generally we observed that thereproducibility of most of the properties is much easier usingdifferent basis sets compared to using different functionalmethods as a result of significant geometrical changes whichis possible especially if there are many light atoms likehydrogen atoms as in themodelsThe order of the energy andthe thermodynamic properties are found to be reproducibleusing different functionalmethods and basis sets butHOMOLUMO 119869-coupling hyperpolarizabilities and isotropic andanisotropic shielding are found to depend more on the typeof the functional used rather than on the type of the basis setThe only significant similarity observed among the methodsapplied in computing hyperpolarizabilities is that they allrated models Ru-S Ru-Cl and Ru-O among their best threeThe optimized geometries and the thermodynamic proper-ties obtained from the functional PBE are found to be verysimilar to MP2 and perform better than B3LYP and CCSDwhich further give insight into many literaturesrsquo preferencefor PBE in optimizing metal complexes In computation ofthe isotropic and anisotropic shielding tensors B3LYP gives
values similar to MP2 and performs better than PBE The IRvibrations and assignment clearly show that the vibrationsobtained from the MP2 and CCSD methods are very similarand give preference to the torsional and bending vibrationsof the molecules over their stretching The order of the IRvibrations of the ruthenium-ligand bonds can be assumed asRu-N gt Ru-O gt Ru-C gt Ru-Cl gt Ru-S gt Ru-P
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
The authors gracefully acknowledged the financial support ofGovan Mbeki Research and Development Centre Universityof Fort Hare South Africa The CHPC in Republic ofSouth Africa is gracefully acknowledged for providing thecomputing facilities and some of the software used for thecomputation
References
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2
(Cpand = 1205785-1-methoxy-24-di-tert-butyl-3-neopentylcyclopenta-dienyl)rdquo Organometallics vol 27 no 3 pp 423ndash429 2008
[2] M A Furrer F Schmitt M Wiederkehr L Juillerat-Jeanneretand B Therrien ldquoCellular delivery of pyrenyl-arene rutheniumcomplexes by a water-soluble arene ruthenium metalla-cagerdquoDalton Transactions vol 41 no 24 pp 7201ndash7211 2012
[3] Q ZhouW Lei YChen et al ldquoRuthenium(II)-arene complexeswith strong fluorescence insight into the underlying mecha-nismrdquoChemistrymdashA European Journal vol 18 no 28 pp 8617ndash8621 2012
[4] L Bıro E Farkas and P Buglyo ldquoHydrolytic behaviour andchloride ion binding capability of [Ru(1205786 minus119901minus cym)(H
2O)3]2+
a solution equilibrium studyrdquoDalton Transactions vol 41 no 1pp 285ndash291 2012
[5] Y Boutadla D L Davies R C Jones and K Singh ldquoThescope of ambiphilic acetate-assisted cyclometallation with half-sandwich complexes of iridium rhodium and rutheniumrdquoChemistrymdashA European Journal vol 17 no 12 pp 3438ndash34482011
[6] Y F Han H Li Y Fei Y J Lin W Z Zhang and GX Jin ldquoSynthesis and structural characterization of binuclearhalf-sandwich iridium rhodium and ruthenium complexescontaining 441015840-dipyridyldisulfide (4DPDS) ligandsrdquo DaltonTransactions vol 39 no 30 pp 7119ndash7124 2010
[7] B Dutta B F Curchod P Campomanes et al ldquoReactions ofalkynes with [RuCl(cyclopentadienyl)] complexes the impor-tant first stepsrdquo ChemistrymdashA European Journal vol 16 no 28pp 8400ndash8409 2010
[8] M Jimenez-Tenorio M C Puerta P Valerga S MonchoG Ujaque and A Lledos ldquoProton-transfer reactions to half-sandwich ruthenium trihydride complexes bearing hemilabilePN ligands experimental and density functional theory stud-iesrdquo Inorganic Chemistry vol 49 no 13 pp 6035ndash6057 2010
14 Journal of Chemistry
[9] B Dutta C Scolaro R Scopelliti P J Dyson and K Sev-erin ldquoImportance of the 120587-ligand remarkable effect of thecyclopentadienyl ring on the cytotoxicity of ruthenium PTAcompoundsrdquoOrganometallics vol 27 no 7 pp 1355ndash1357 2008
[10] T Bugarcic A Habtemariam J Stepankova et al ldquoThe con-trasting chemistry and cancer cell cytotoxicity of bipyridineand bipyridinediol ruthenium(II) arene complexesrdquo InorganicChemistry vol 47 no 24 pp 11470ndash11486 2008
[11] M Castellano-Castillo H Kostrhunova V Marini et al ldquoBind-ing ofmismatch repair proteinMutS tomispairedDNA adductsof intercalating ruthenium(II) arene complexesrdquo Journal ofBiological Inorganic Chemistry vol 13 no 6 pp 993ndash999 2008
[12] S J Dougan A Habtemariam S E McHale S Parsons andP J Sadler ldquoCatalytic organometallic anticancer complexesrdquoProceedings of the National Academy of Sciences of the UnitedStates of America vol 105 no 33 pp 11628ndash11633 2008
[13] S J Dougan M Melchart A Habtemariam S Parsons and PJ Sadler ldquoPhenylazo-pyridine and phenylazo-pyrazole chloridoruthenium(II) arene complexes arene loss aquation and can-cer cell cytotoxicityrdquo Inorganic Chemistry vol 45 no 26 pp10882ndash10894 2006
[14] V Ritleng P Bertani M Pfeffer C Sirlin and J HirschingerldquoOptically active ortho-metalated half-sandwich rutheniumcomplexes solid-state NMR as a convenient tool to analyzemixtures of diastereomersrdquo Inorganic Chemistry vol 40 no 20pp 5117ndash5122 2001
[15] Y Sunada Y Hayashi H Kawaguchi and K TatsumildquoAlkynethiolato and alkyneselenolato rutheniumhalf-sandwichcomplexes Synthesis structures and reactions with (1205785ndashC5H5)2Zrrdquo Inorganic Chemistry vol 40 no 27 pp 7072ndash70782001
[16] K Yamanari R Ito S Yamamoto et al ldquoCyclic tetramerscomposed of rhodium(III) iridium(III) or ruthenium(II) half-sandwich and6-purinethionesrdquo Inorganic Chemistry vol 41 no25 pp 6824ndash6830 2002
[17] F Caruso M Rossi A Benson et al ldquoRuthenium-arenecomplexes of curcumin X-ray and density functional the-ory structure synthesis and spectroscopic characterizationin vitro antitumor activity and DNA docking studies of (p-cymene)Ru(curcuminato)chlorordquo Journal of Medicinal Chem-istry vol 55 no 3 pp 1072ndash1081 2012
[18] C Gossens I Tavernelli and U Rothlisberger ldquoBinding oforganometallic ruthenium(II) anticancer compounds to nucle-obases a computational studyrdquo Journal of Physical Chemistry Avol 113 no 43 pp 11888ndash11897 2009
[19] A M Pizarro A Habtemariam and P J Sadler ldquoActiva-tion mechanisms for organometallic anticancer complexesrdquoin Medicinal Organometallic Chemistry vol 32 of Topics inOrganometallic Chemistry pp 21ndash56 Springer Berlin Ger-many 2010
[20] I Turel and J Kljun ldquoInteractions of metal ions with DNAits constituents and derivatives which may be relevant foranticancer researchrdquoCurrent Topics inMedicinal Chemistry vol11 no 21 pp 2661ndash2687 2011
[21] G Gasser I Ott and N Metzler-Nolte ldquoOrganometallic anti-cancer compoundsrdquo Journal of Medicinal Chemistry vol 54 no1 pp 3ndash25 2011
[22] K J Kilpin S Crot T Riedel J A Kitchen and P JDyson ldquoRuthenium(II) and osmium(II) 123-triazolylideneorganometallics a preliminary investigation into the biologicalactivity of rsquoclickrsquo carbene complexesrdquo Dalton Transactions vol43 no 3 pp 1443ndash1448 2014
[23] A F A Peacock S Parsons and P J Sadler ldquoTuning thehydrolytic aqueous chemistry of osmium arene complexeswith NO-chelating ligands to achieve cancer cell cytotoxicityrdquoJournal of the American Chemical Society vol 129 no 11 pp3348ndash3357 2007
[24] A F A Peacock M Melchart R J Deeth A Habtemariam SParsons and P J Sadler ldquoOsmium(II) and ruthenium(II) arenemaltolato complexes rapid hydrolysis and nucleobase bindingrdquoChemistrymdashA European Journal vol 13 no 9 pp 2601ndash26132007
[25] F Pelletier V Comte A Massard et al ldquoDevelopment ofbimetallic titanoceneminusrutheniumminusarene complexes as anti-cancer agents relationships between structural and biologicalpropertiesrdquo Journal of Medicinal Chemistry vol 53 no 19 pp6923ndash6933 2010
[26] K J Kilpin and P J Dyson ldquoEnzyme inhibition by metalcomplexes concepts strategies and applicationsrdquo ChemicalScience vol 4 no 4 pp 1410ndash1419 2013
[27] G Gasser andNMetzler-Nolte ldquoThe potential of organometal-lic complexes in medicinal chemistryrdquo Current Opinion inChemical Biology vol 16 no 1-2 pp 84ndash91 2012
[28] I Turel J Kljun F Perdih et al ldquoFirst ruthenium organometal-lic complex of antibacterial agent ofloxacin Crystal structureand interactions with DNArdquo Inorganic Chemistry vol 49 no23 pp 10750ndash10752 2010
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[31] W J Stevens M Krauss H Basch and P G Jasien ldquoRelativisticcompact effective potentials and efficient shared-exponentbasis sets for the third- fourth- and fifth-row atomsrdquoCanadianJournal of Chemistry vol 70 no 2 pp 612ndash630 1992
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[33] D J Feller ldquoThe role of databases in support of computationalchemistry calculationsrdquo Journal of Computational Chemistryvol 17 no 13 pp 1571ndash1586 1996
[34] K L Schuchardt B T Didier T Elsethagen et al ldquoBasis setexchange a community database for computational sciencesrdquoJournal of Chemical Information andModeling vol 47 no 3 pp1045ndash1052 2007
[35] Y Liu C-G Liu S-L Sun G-C Yang and Y-Q QiuldquoRedox-switching second-order nonlinear optical responses ofNandNandN ruthenium complexesrdquo Computational and TheoreticalChemistry vol 979 pp 112ndash118 2012
[36] P S Liyanage R M de Silva and K M N de Silva ldquoNonlinearoptical (NLO) properties of novel organometallic complexeshigh accuracy density functional theory (DFT) calculationsrdquoJournal of Molecular Structure THEOCHEM vol 639 pp 195ndash201 2003
[37] MH Jamroz ldquoVibrational EnergyDistributionAnalysis VEDA4 ProgramrdquoWarsaw Poland 2004ndash2010 httpwwwsmmgpl
[38] M H Jamroz J C Dobrowolski and R Brzozowski ldquoVibra-tional modes of 26- 27- and 23-diisopropylnaphthalene ADFT studyrdquo Journal of Molecular Structure vol 787 no 1ndash3 pp172ndash183 2006
[39] M H Jamroz ldquoVibrational Energy Distribution Analysis(VEDA) scopes and limitationsrdquo Spectrochimica Acta AMolec-ular and Biomolecular Spectroscopy vol 114 pp 220ndash230 2013
Journal of Chemistry 15
[40] R Marchal P Carbonniere D Begue and C Pouchan ldquoStruc-tural and vibrational determination of small galliumndasharsenideclusters fromCCSD(T) andDFT calculationsrdquoChemical PhysicsLetters vol 453 no 1ndash3 pp 49ndash54 2008
[41] R Marchal P Carbonniere and C Pouchan ldquoStructural andvibrational properties prediction of Sn
119899Te119899clusters (n = 2ndash
8) using the GSAM approachrdquo Computational and TheoreticalChemistry vol 990 pp 100ndash105 2012
[42] T Helgaker M Jaszunski and M Pecul ldquoThe quantum-chemical calculation of NMR indirect spin-spin coupling con-stantsrdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 53 no 4 pp 249ndash268 2008
[43] F A Perras andD L Bryce ldquoTheoretical study of homonuclear Jcoupling between quadrupolar spins single-crystal DOR andJ-resolved NMRrdquo Journal of Magnetic Resonance vol 242 pp23ndash32 2014
[44] I D Burns A F Hill A J P White D J Williams and J DE T Wilton-Ely ldquoPolyazolyl chelate chemistry 61 bidentatecoordination of HB(pz)
3(pz = Pyrazol-1-yl) to ruthenium and
osmium crystal structure of [RuH(CO)(PPh3)2k2-HB(pz)
3]rdquo
Organometallics vol 17 no 8 pp 1552ndash1557 1998[45] M Al-Noaimi and M A AlDamen ldquoRuthenium complexes
incorporating azoimine and 120572-diamine based ligands synthe-sis crystal structure electrochemistry and DFT calculationrdquoInorganica Chimica Acta vol 387 pp 45ndash51 2012
[46] K Nakajima Y Ando H Mano and M Kojima ldquoPhotosub-stitution reactivity crystal structures and electrochemistry ofruthenium(II) (III) complexes containing tetradentate (O
2N2
S2N2 and P
2N2) Schiff base ligandsrdquo Inorganica Chimica Acta
vol 274 no 2 pp 184ndash191 1998[47] Z-L Lu K Eichele I Warad et al ldquoSupported organometal-
lic complexes XXXVIII [1] Bis(methoxyethyldimethlphos-phine)ruthenium(II) complexes as transfer hydrogenation cat-alystsrdquo Zeitschrift fur Anorganische und Allgemeine Chemie vol629 no 7-8 pp 1308ndash1315 2003
[48] R Gaur and L Mishra ldquoSynthesis and characterization ofRu(II)ndashDMSOndashClndashchalcone complexes DNA binding nucle-ase and topoisomerase II inhibitory activityrdquo Inorganic Chem-istry vol 51 no 5 pp 3059ndash3070 2012
[49] B Cebrian-Losantos E Reisner C R Kowol et al ldquoSynthesisand reactivity of the aquation product of the antitumor complextrans-[Ru IIICI
4(indazole)
2] minusrdquo Inorganic Chemistry vol 47 no
14 pp 6513ndash6523 2008[50] B T Rasley M Rapta and R J Kulawiec ldquoDiastereoselectivity
in enolate coordination in a new class of chiral rutheniumenolate complexesrdquo Organometallics vol 15 no 13 pp 2852ndash2854 1996
[51] S David R S Perkins F R Fronczek S Kasiri S S MandalandR S Srivastava ldquoSynthesis characterization and anticanceractivity of ruthenium-pyrazole complexesrdquo Journal of InorganicBiochemistry vol 111 pp 33ndash39 2012
[52] B Dutta E Solari S Gauthier R Scopelliti and K SeverinldquoRuthenium half-sandwich complexes with sterically demand-ing cyclopentadienyl ligandsrdquo Organometallics vol 26 no 19pp 4791ndash4799 2007
[53] G Turkoglu S Tampier F Strinitz F W Heinemann E Hub-ner and N Burzlaff ldquoRuthenium carbonyl complexes bearingbis(pyrazol-1-yl)carboxylato ligandsrdquo Organometallics vol 31no 6 pp 2166ndash2174 2012
[54] A K Renfrew A D Phillips E Tapavicza R ScopellitiU Rothlisberger and P J Dyson ldquoTuning the efficacy of
ruthenium(II)-arene (RAPTA) antitumor compounds with flu-orinated arene ligandsrdquo Organometallics vol 28 no 17 pp5061ndash5071 2009
[55] P M Jeffries R E Ellenwood and G S Girolami ldquoAnionicruthenium(II) alkyls with ancillary diene and dienyl ligandssynthesis and structures of [(12057821205782-C
7H8)RuMe
4]2minus and [(12057831205782-
C8H11)RuMe
3]2minusrdquo Inorganica Chimica Acta vol 361 no 1 pp
3165ndash3170 2008[56] B R James D Dolphin T W Leung F W B Einstein
and A C Willis ldquoPreparation and characterization of someruthenium(III) porphyrins including the crystal structure ofbromo(octaethylporphinato)(triphenylphosphine)ruthenium(III)rdquoCanadian Journal of Chemistry vol 62 no 7 pp 1238ndash12451984
[57] M Plois R Wolf W Hujo and S Grimme ldquoTowards reagentsfor bimetallic activation reactions polyhydride complexes withRu2H3 Ru2ZnH6 and Cu
2Ru2H6coresrdquo European Journal of
Inorganic Chemistry vol 2013 no 17 pp 3039ndash3048 2013[58] L Hintermann L Xiao A Labonne and U Englert
ldquo[CpRu(1205786-naphthalene)]PF6as precursor in complex synthesis
and catalysis with the cyclopentadienyl-ruthenium(II) cationrdquoOrganometallics vol 28 no 19 pp 5739ndash5748 2009
[59] I W Wyman K N Robertson T S Cameron J C SwartsandM A S Aquino ldquoSynthesis structure and electrochemistryof (ferrocene-2-propenoato-OO1015840)bis[12-bis(diphenylphosphi-no)ethane-PP1015840]ruthenium(II) hexafluorophosphaterdquo Inorgan-ica Chimica Acta vol 359 no 9 pp 3092ndash3096 2006
[60] C A Vock C Scolaro A D Phillips R Scopelliti G Sava andP J Dyson ldquoSynthesis characterization and in vitro evaluationof novel ruthenium(II) 1205786-arene imidazole complexesrdquo Journalof Medicinal Chemistry vol 49 no 18 pp 5552ndash5561 2006
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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CatalystsJournal of
Journal of Chemistry 7
Table9Th
efirsth
yperpo
lariz
ability(szlig)inesu(1times10minus30)v
aluesa
tdifferentcom
putatio
nalm
etho
ds
MP2
aug-cc-pV
TZMP2
DGDZV
PMP2
SBK
JCVDZ
CCSD
DGDZV
PCC
SDSBK
JCVDZ
PBEDGDZV
PPB
ESB
KJCVDZ
B3LY
PDGDZV
PB3
LYPSB
KJCVDZ
Ru-C
153
179
171
108
098
244
028
055
055
Ru-N
569
224
380
105
109
077
063
076
062
Ru-O
3505
1791
1860
822
548
178
160
220
205
Ru-C
l1173
1440
1325
558
547
284
289
325
313
Ru-P
177
180
213
124
151
152
147
135
137
Ru-S
28214
33591
11477
8295
315
214
182
207
165
8 Journal of Chemistry
Table10Th
ecorrelationwith
inthed
ifferentm
etho
dsused
incompu
tingthefi
rsth
yperpo
lariz
abilitie
s
MP2
aug-cc-pV
TZMP2
DGDZV
PMP2
SBK
JCVDZ
CCSD
DGDZV
PCC
SDSBK
JCVDZ
PBEDGDZV
PPB
ESB
KJCVDZ
B3LY
PDGDZV
PB3
LYPSB
KJCVDZ
MP2
-acc
100
100
100
004
014
019
030
024
010
MP2
-dv
100
100
100
minus001
010
020
029
022
009
MP2
-ecp
100
100
100
minus005
006
019
027
019
006
CCSD
-dv
004
minus001
minus005
100
095
031
062
075
075
CCSD
-ECP
014
010
006
095
100
045
081
092
091
PBE-dv
019
020
019
031
045
100
042
051
053
PBE-EC
P030
029
027
062
081
042
100
097
095
B3LY
P-dv
024
022
019
075
092
051
097
100
099
B3LY
P-EC
P010
009
006
075
091
053
095
099
100
Journal of Chemistry 9
200 300 400 500 600 700200 300 400 500 600 700
200 300 400 500 600 700200 300 400 500 600 700
200 300 400 500 600 700200 300 400 500 600 700
Ru-C-MP2Ru-C-CCSD
Ru-C-PBE0Ru-C-B3LYP
Ru-N-MP2Ru-N-CCSD
Ru-N-PBE0Ru-N-B3LYP
Ru-O-MP2Ru-O-CCSD
Ru-O-PBE0Ru-O-B3LYP
Ru-Cl-MP2Ru-Cl-CCSD
Ru-Cl-PBE0Ru-Cl-B3LYP
Ru-P-MP2Ru-P-CCSD
Ru-P-PBE0Ru-P-B3LYP
Ru-S-MP2Ru-S-CCSD
Ru-S-PBE0Ru-S-B3LYP
Figure 3 The IR vibrations of the six models computed using MP2 (black) CCSD (red) PBE (green) and B3LYP (blue)
10 Journal of Chemistry
Table11Th
eIRvibrations
oftheR
u-Lbo
ndsa
tdifferentcom
putatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
6077
72349120573(H
RuH)120592(Ru-C)
5872
73346120592(Ru-C)
68224
195
120592(Ru-C)
63297
226
120573(H
RuH)120592(Ru-C)
50222
238
120591(H
RuCH
)120592(Ru-C)
53062
71120573(H
RuH)120592(Ru-C)
Ru-N
71899
977
120592(Ru-N)120592(Ru-H)
62352
1636120592(Ru-N)
66265
2879120573(H
RuH)120592(Ru-N)
71495
1013
120592(Ru-N)
48235
101120592(Ru-N)
49539
738
120592(Ru-N)
65608
137
120573(H
RuH)120592(Ru-N)
Ru-O
7178
11371
120592(Ru-O)
63412
1586120592(Ru-O)
70574
75120592(Ru-O)
68889
2395
120592(Ru-O)
Ru-C
l43529
2195
120592(Ru-Cl)
5913
3644
120592(Ru-Cl)
65732
376
120592(Ru-Cl)
32331
1022
120592(Ru-Cl)
4478
43433
120592(Ru-Cl)
Ru-P
28203
171
120592(Ru-P)
2393
9395
120592(Ru-P)
44535
232
120592(Ru-P)
2793
71025
o(Ru
HPH
)120592(Ru-P)
23442
711
o(Ru
HPH
)120592(Ru-P)
Ru-S
4119
4401
120592(Ru-S)
32619
424
120592(Ru-S)
3574
92496
o(Ru
HSH
)120592(Ru-S)
40866
311
120592(Ru-S)
37311
597
o(Ru
HSH
)120592(Ru-S)
38596
1999
120592(Ru-S)
120592isstr
etching120573isbend
ing120591istorsionalandoisou
t-of-p
lane
torsional
Journal of Chemistry 11
Table12Th
eassignm
ento
fthe
prom
inentIRvibrations
ofthem
odels
atdifferent
compu
tatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
346783
9624120573(H
RuH)120592(Ru-H)
386628
124120573(H
RuH)120573(H
RuH)
120592(C
H)120592(Ru-H)
381759
1510
1120573(H
RuH)120573(H
RuH)
120591(H
RuHC)
30511
103120592(C
H)o(Ru
HCH
)120592(C
H)
313241
8772
120592(C
H)120592(C
H)
344585
6003
120592(Ru-H)
326534
582120573(H
CH)120592(C
H)120592(Ru-H)
3044
61
5191120592(C
H)o(Ru
HCH
)120592(Ru-H)
306501
5614120573(H
RuH)120573(H
RuH)
o(Ru
HCH
)323718
7402120573(H
CH)120573(H
RuH)120592(C
H)
310576
7913
120573(H
RuH)120592(Ru-H)
29104116677
120592(C
H)120592(C
H)
299873
14381
120592(C
H)120592(C
H)
310607
10481120573(H
RuC)
120591(H
CRuH
)o(Ru
HCH
)230969
6851120573(H
RuH)120591(H
RuHC)
120592(Ru-H)
247128
4498120573(H
RuH)o(Ru
HCH
)120592(Ru-H)
240085
1095
1120592(C
H)
231944
1014
7120573(H
RuC)
o(RuH
CH)
207553
969120573(H
RuH)120573(H
RuH)
120592(Ru-H)120592(Ru-H)
232314
1296
8120592(C
H)
Ru-N
38020714205120573(H
RuH)120573(H
RuH)
120573(H
RuH)
401043
1231120573(H
RuH)120591(H
RuHN)
120592(N
H)
403478
11428120591(H
RuNH)o(Ru
HNH)
120592(N
H)
353289
10673120573(H
RuH)120573(H
RuH)
339019
20019
120592(N
H)120592(N
H)
347897
18119120573(H
RuH)120573(H
RuH)
120591(H
RuHN)120592(Ru-H)
347497
1866120573(H
RuH)120573(H
RuH)
120592(Ru-H)
331504
19282
120592(N
H)120592(N
H)
32687139839
120592(N
H)120592(N
H)
336728
2897
5120592(Ru-H)
332695
1499
5120573(H
RuH)o(Ru
HNH)
318372
37524
120592(N
H)120592(N
H)
293151
4214120592(Ru-H)120592(Ru-H)120592(N
H)
120592(N
H)
327085
3514120573(H
RuH)120591(H
RuHN)
120592(Ru-H)
2746
17455
o(Ru
HNH)120592(Ru-H)
120592(Ru-H)
238961
4007120573(H
RuH)120592(Ru-H)
207916
6108
120592(Ru-H)
199979
4338
120573(H
NH)
210524
6443
o(Ru
HNH)120592(N
H)
120592(Ru-H)
203734
6557
120592(Ru-H)
Ru-O
372613
2694
9120592(O
H)
380749
28041
o(Ru
HOH)120592(Ru-H)
389061
1005
o(Ru
HOH)120573(H
RuH)
3608772399
3120592(O
H)
275932
1407120573(H
RuH)o(Ru
HOH)
o(Ru
HOH)120592(Ru-H)
31079
1921120573(H
RuO)120573(H
RuH)
o(Ru
HOH)
370979
51891120573(H
RuO)120573(H
RuO)
327956
2992120573(H
RuH)120573(H
RuH)
18598
2333
120592(Ru-H)120592(Ru-H)
179443
2374120573(H
RuH)o(Ru
HOH)
120592(Ru-H)
291506
5502
o(Ru
HOH)120592(Ru-H)
120592(Ru-H)
220079
1599120573(H
RuH)o(Ru
HOH)
120592(Ru-H)120592(Ru-H)
1346
08
2894120592(Ru-H)120592(Ru-H)
125632
2895120592(Ru-H)120573(H
ORu
)260461
4569120592(O
H)120573(H
ORu
)203014
1588
120592(Ru-H)
112741
9479120573(H
RuH)120592(Ru-H)
120592(Ru-H)
109235
7374
120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
205106
3383120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
147934
29120592(Ru-H)120592(Ru-H)
Ru-C
l185546
2458
120592(Ru-H)
308667
1411120573(H
RuH)o(Ru
HClH)
120592(Ru-H)
30365123653
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
22088
2242
120592(Ru-H)
131751
3288
120592(Ru-H)
179947
2511
o(Ru
HClH)120592(Ru-H)
120592(Ru-H)
261179
3015
120592(Ru-H)120573(H
RuH)
210816
1124
120592(Ru-H)
114581
9421
120592(Ru-H)
121159
3269120573(H
RuH)120573(H
RuH)
120573(H
RuCl)
20399
3006120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
203112
1687
120592(Ru-H)
84759
3157
120592(Ru-H)
110861
7222
o(Ru
HClH)o(Ru
HClH)
120592(Ru-H)120573(H
RuCl)
131224
3565
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
147293
3151
120592(Ru-H)
79488
381
120573(H
RuH)
7687
2483120573(H
RuH)120592(Ru-H)
120592(Ru-H)120592(Ru-H)
109164
1501120592(Ru-H)120573(H
RuH)
11346
9195
3120573(H
RuH)
12 Journal of Chemistry
Table12C
ontin
ued
B3LY
PCC
SDMP2
PBE
Ru-P
384575
1547
120573(H
RuH)
40856716207120573(H
RuH)120591(H
RuPH
)o(Ru
HPH
)410148
11361120573(H
RuH)120573(H
RuH)
3509879645120573(H
RuH)120592(Ru-H)
296363
1457120573(H
RuH)120592(Ru-H)
328227
1508120573(H
RuH)120573(H
RuH)
120591(H
PRuH
)264975
4273
120573(H
RuP)120592(Ru-H)
246259
4871
120592(PH)120592(PH)
253628
4006
120592(PH)120592(PH)
261721
3138
120592(Ru-H)
262336
4752
120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
24307
5689
120592(PH)120592(PH)
250603
4624
120592(PH)120592(PH)
259379
3579
120573(H
RuP)
256933
4865120573(H
RuP)120573
(HRu
H)
238468
1306120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
245899
7096
120592(PH)120592(PH)
255419
4427120573(H
RuH)120591(H
PRuH
)120591(H
PRuH
)228633
8692
120573(H
RuH)120592(PH)
237354
92120592(PH)
Ru-S
265041
1308
120592(SH)
290793
378120573(H
RuH)120591(H
SRuH
)120592(Ru-H)120573(H
RuS)
417199
15487
o(Ru
HSH
)o(Ru
HSH
)120573(H
RuH)
34606
2384120573(H
RuH)120573(H
RuH)
120573(H
RuH)o(Ru
HSH
)
26342
1916
120573(H
RuH)120592(Ru-H)
188073
1685120573(H
RuH)120573(H
RuH)
120592(Ru-H)
28041
199265120573(H
RuS)120573
(HRu
H)
120573(H
RuH)120592(Ru-H)
258225
1254
120592(SH)
1913
1699
120592(Ru-H)
114853
2967120591(H
SRuH
)120592(SH)
120592(Ru-H)
2385442392374
120573(H
RuS)
21675
2604
120592(Ru-H)
121642
3386120592(Ru-H)120592(Ru-H)
109859
10132120573(H
RuH)120591(H
SRuH
)o(Ru
HSH
)120592(Ru-H)
225761
44894
120592(Ru-H)120573(H
RuH)
132047
3699120592(Ru-H)120592(Ru-H)
11086
11006120573(H
RuH)120592(Ru-H)
82534
331120591(H
SRuH
)120592(Ru-H)
120592(Ru-H)
210643
5205
120592(Ru-H)
8835
5098
o(Ru
HSH
)o(Ru
HSH
)120592(Ru-H)120592(Ru-H)
Journal of Chemistry 13
all the methods Ru-C Ru-N and Ru-O vibrations are withinthe range of 500 to 720 which is far higher than the rangeof vibrations of Ru-Cl Ru-P and Ru-S which are foundwithin the range of 224 to 658 Generally the order of Ru-L vibrations can be assumed as Ru-N gt Ru-O gt Ru-C gtRu-Cl gt Ru-S gt Ru-P (Table 11) The wavenumbers of thevibrations computed from the different methods appear to besignificantly different from each other in values and positions(Figure 3) The features of the IR spectra using MP2 andCCSD are very similar in the models Some vibration around291506 in model Ru-O 303651 in Ru-Cl and 238544 inRu-S are very prominent in MP2 methods compared to inany other methods or even absent in other methods Forinstance the bending of the angle of HRuS which is found tobe prominent in MP2 method is completely absent in othermethods (see Figure 3 and Table 12) The MP2 and CCSDshow strong vibrations within the range of 3800 to 4100 inmany of the models which are obviously absent in manyof the PBE and B3LYP methods Using the PED methodas implemented in VEDA package most of these vibrationsat high frequencies are a result of the torsional and out-of-plane vibration of H-Ru-X-H where X represents the typeof the model as shown in Table 12 In addition most of thebending vibrations which are determined by PBE and B3LYPfrom 2800 to 3800 in the models are also determined byMP2 and CCSD though some cases are at lower wavenumbercompared to PBE and B3LYP (Table 12) In the models Ru-Oand Ru-Cl PBE and B3LYP give priority to the OH and RuHvibrations respectively whileMP2 andCCSD give priority tothe torsional stretching and angle bending of their atoms
4 Conclusions
Six models of Ru-L bonds Ru-C Ru-N Ru-O Ru-Cl Ru-P and Ru-S are built to represent common rutheniumcomplexes and possible ruthenium-receptor interactionsThe reproducibility of their geometrical electronic spec-troscopic and conductive properties was investigated usingMP2 CCSD PBE and B3LYP functionals with differentcombination of basis sets Generally we observed that thereproducibility of most of the properties is much easier usingdifferent basis sets compared to using different functionalmethods as a result of significant geometrical changes whichis possible especially if there are many light atoms likehydrogen atoms as in themodelsThe order of the energy andthe thermodynamic properties are found to be reproducibleusing different functionalmethods and basis sets butHOMOLUMO 119869-coupling hyperpolarizabilities and isotropic andanisotropic shielding are found to depend more on the typeof the functional used rather than on the type of the basis setThe only significant similarity observed among the methodsapplied in computing hyperpolarizabilities is that they allrated models Ru-S Ru-Cl and Ru-O among their best threeThe optimized geometries and the thermodynamic proper-ties obtained from the functional PBE are found to be verysimilar to MP2 and perform better than B3LYP and CCSDwhich further give insight into many literaturesrsquo preferencefor PBE in optimizing metal complexes In computation ofthe isotropic and anisotropic shielding tensors B3LYP gives
values similar to MP2 and performs better than PBE The IRvibrations and assignment clearly show that the vibrationsobtained from the MP2 and CCSD methods are very similarand give preference to the torsional and bending vibrationsof the molecules over their stretching The order of the IRvibrations of the ruthenium-ligand bonds can be assumed asRu-N gt Ru-O gt Ru-C gt Ru-Cl gt Ru-S gt Ru-P
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
The authors gracefully acknowledged the financial support ofGovan Mbeki Research and Development Centre Universityof Fort Hare South Africa The CHPC in Republic ofSouth Africa is gracefully acknowledged for providing thecomputing facilities and some of the software used for thecomputation
References
[1] B Dutta R Scopelliti and K Severin ldquoSynthesis structure andreactivity of the methoxy-bridged dimer [CpandRu(120583-OMe)]
2
(Cpand = 1205785-1-methoxy-24-di-tert-butyl-3-neopentylcyclopenta-dienyl)rdquo Organometallics vol 27 no 3 pp 423ndash429 2008
[2] M A Furrer F Schmitt M Wiederkehr L Juillerat-Jeanneretand B Therrien ldquoCellular delivery of pyrenyl-arene rutheniumcomplexes by a water-soluble arene ruthenium metalla-cagerdquoDalton Transactions vol 41 no 24 pp 7201ndash7211 2012
[3] Q ZhouW Lei YChen et al ldquoRuthenium(II)-arene complexeswith strong fluorescence insight into the underlying mecha-nismrdquoChemistrymdashA European Journal vol 18 no 28 pp 8617ndash8621 2012
[4] L Bıro E Farkas and P Buglyo ldquoHydrolytic behaviour andchloride ion binding capability of [Ru(1205786 minus119901minus cym)(H
2O)3]2+
a solution equilibrium studyrdquoDalton Transactions vol 41 no 1pp 285ndash291 2012
[5] Y Boutadla D L Davies R C Jones and K Singh ldquoThescope of ambiphilic acetate-assisted cyclometallation with half-sandwich complexes of iridium rhodium and rutheniumrdquoChemistrymdashA European Journal vol 17 no 12 pp 3438ndash34482011
[6] Y F Han H Li Y Fei Y J Lin W Z Zhang and GX Jin ldquoSynthesis and structural characterization of binuclearhalf-sandwich iridium rhodium and ruthenium complexescontaining 441015840-dipyridyldisulfide (4DPDS) ligandsrdquo DaltonTransactions vol 39 no 30 pp 7119ndash7124 2010
[7] B Dutta B F Curchod P Campomanes et al ldquoReactions ofalkynes with [RuCl(cyclopentadienyl)] complexes the impor-tant first stepsrdquo ChemistrymdashA European Journal vol 16 no 28pp 8400ndash8409 2010
[8] M Jimenez-Tenorio M C Puerta P Valerga S MonchoG Ujaque and A Lledos ldquoProton-transfer reactions to half-sandwich ruthenium trihydride complexes bearing hemilabilePN ligands experimental and density functional theory stud-iesrdquo Inorganic Chemistry vol 49 no 13 pp 6035ndash6057 2010
14 Journal of Chemistry
[9] B Dutta C Scolaro R Scopelliti P J Dyson and K Sev-erin ldquoImportance of the 120587-ligand remarkable effect of thecyclopentadienyl ring on the cytotoxicity of ruthenium PTAcompoundsrdquoOrganometallics vol 27 no 7 pp 1355ndash1357 2008
[10] T Bugarcic A Habtemariam J Stepankova et al ldquoThe con-trasting chemistry and cancer cell cytotoxicity of bipyridineand bipyridinediol ruthenium(II) arene complexesrdquo InorganicChemistry vol 47 no 24 pp 11470ndash11486 2008
[11] M Castellano-Castillo H Kostrhunova V Marini et al ldquoBind-ing ofmismatch repair proteinMutS tomispairedDNA adductsof intercalating ruthenium(II) arene complexesrdquo Journal ofBiological Inorganic Chemistry vol 13 no 6 pp 993ndash999 2008
[12] S J Dougan A Habtemariam S E McHale S Parsons andP J Sadler ldquoCatalytic organometallic anticancer complexesrdquoProceedings of the National Academy of Sciences of the UnitedStates of America vol 105 no 33 pp 11628ndash11633 2008
[13] S J Dougan M Melchart A Habtemariam S Parsons and PJ Sadler ldquoPhenylazo-pyridine and phenylazo-pyrazole chloridoruthenium(II) arene complexes arene loss aquation and can-cer cell cytotoxicityrdquo Inorganic Chemistry vol 45 no 26 pp10882ndash10894 2006
[14] V Ritleng P Bertani M Pfeffer C Sirlin and J HirschingerldquoOptically active ortho-metalated half-sandwich rutheniumcomplexes solid-state NMR as a convenient tool to analyzemixtures of diastereomersrdquo Inorganic Chemistry vol 40 no 20pp 5117ndash5122 2001
[15] Y Sunada Y Hayashi H Kawaguchi and K TatsumildquoAlkynethiolato and alkyneselenolato rutheniumhalf-sandwichcomplexes Synthesis structures and reactions with (1205785ndashC5H5)2Zrrdquo Inorganic Chemistry vol 40 no 27 pp 7072ndash70782001
[16] K Yamanari R Ito S Yamamoto et al ldquoCyclic tetramerscomposed of rhodium(III) iridium(III) or ruthenium(II) half-sandwich and6-purinethionesrdquo Inorganic Chemistry vol 41 no25 pp 6824ndash6830 2002
[17] F Caruso M Rossi A Benson et al ldquoRuthenium-arenecomplexes of curcumin X-ray and density functional the-ory structure synthesis and spectroscopic characterizationin vitro antitumor activity and DNA docking studies of (p-cymene)Ru(curcuminato)chlorordquo Journal of Medicinal Chem-istry vol 55 no 3 pp 1072ndash1081 2012
[18] C Gossens I Tavernelli and U Rothlisberger ldquoBinding oforganometallic ruthenium(II) anticancer compounds to nucle-obases a computational studyrdquo Journal of Physical Chemistry Avol 113 no 43 pp 11888ndash11897 2009
[19] A M Pizarro A Habtemariam and P J Sadler ldquoActiva-tion mechanisms for organometallic anticancer complexesrdquoin Medicinal Organometallic Chemistry vol 32 of Topics inOrganometallic Chemistry pp 21ndash56 Springer Berlin Ger-many 2010
[20] I Turel and J Kljun ldquoInteractions of metal ions with DNAits constituents and derivatives which may be relevant foranticancer researchrdquoCurrent Topics inMedicinal Chemistry vol11 no 21 pp 2661ndash2687 2011
[21] G Gasser I Ott and N Metzler-Nolte ldquoOrganometallic anti-cancer compoundsrdquo Journal of Medicinal Chemistry vol 54 no1 pp 3ndash25 2011
[22] K J Kilpin S Crot T Riedel J A Kitchen and P JDyson ldquoRuthenium(II) and osmium(II) 123-triazolylideneorganometallics a preliminary investigation into the biologicalactivity of rsquoclickrsquo carbene complexesrdquo Dalton Transactions vol43 no 3 pp 1443ndash1448 2014
[23] A F A Peacock S Parsons and P J Sadler ldquoTuning thehydrolytic aqueous chemistry of osmium arene complexeswith NO-chelating ligands to achieve cancer cell cytotoxicityrdquoJournal of the American Chemical Society vol 129 no 11 pp3348ndash3357 2007
[24] A F A Peacock M Melchart R J Deeth A Habtemariam SParsons and P J Sadler ldquoOsmium(II) and ruthenium(II) arenemaltolato complexes rapid hydrolysis and nucleobase bindingrdquoChemistrymdashA European Journal vol 13 no 9 pp 2601ndash26132007
[25] F Pelletier V Comte A Massard et al ldquoDevelopment ofbimetallic titanoceneminusrutheniumminusarene complexes as anti-cancer agents relationships between structural and biologicalpropertiesrdquo Journal of Medicinal Chemistry vol 53 no 19 pp6923ndash6933 2010
[26] K J Kilpin and P J Dyson ldquoEnzyme inhibition by metalcomplexes concepts strategies and applicationsrdquo ChemicalScience vol 4 no 4 pp 1410ndash1419 2013
[27] G Gasser andNMetzler-Nolte ldquoThe potential of organometal-lic complexes in medicinal chemistryrdquo Current Opinion inChemical Biology vol 16 no 1-2 pp 84ndash91 2012
[28] I Turel J Kljun F Perdih et al ldquoFirst ruthenium organometal-lic complex of antibacterial agent ofloxacin Crystal structureand interactions with DNArdquo Inorganic Chemistry vol 49 no23 pp 10750ndash10752 2010
[29] C Adamo and V Barone ldquoToward reliable density functionalmethods without adjustable parameters the PBE0 modelrdquoJournal of Chemical Physics vol 110 no 13 pp 6158ndash6170 1999
[30] A D Becke ldquoDensity-functional thermochemistry IIIThe roleof exact exchangerdquoThe Journal of Chemical Physics vol 98 no7 article 5648 1993
[31] W J Stevens M Krauss H Basch and P G Jasien ldquoRelativisticcompact effective potentials and efficient shared-exponentbasis sets for the third- fourth- and fifth-row atomsrdquoCanadianJournal of Chemistry vol 70 no 2 pp 612ndash630 1992
[32] M J Frisch GW Trucks H B Schlegel et alOfficial Gaussian09 Literature Citation Gaussian Wallingford UK 2009
[33] D J Feller ldquoThe role of databases in support of computationalchemistry calculationsrdquo Journal of Computational Chemistryvol 17 no 13 pp 1571ndash1586 1996
[34] K L Schuchardt B T Didier T Elsethagen et al ldquoBasis setexchange a community database for computational sciencesrdquoJournal of Chemical Information andModeling vol 47 no 3 pp1045ndash1052 2007
[35] Y Liu C-G Liu S-L Sun G-C Yang and Y-Q QiuldquoRedox-switching second-order nonlinear optical responses ofNandNandN ruthenium complexesrdquo Computational and TheoreticalChemistry vol 979 pp 112ndash118 2012
[36] P S Liyanage R M de Silva and K M N de Silva ldquoNonlinearoptical (NLO) properties of novel organometallic complexeshigh accuracy density functional theory (DFT) calculationsrdquoJournal of Molecular Structure THEOCHEM vol 639 pp 195ndash201 2003
[37] MH Jamroz ldquoVibrational EnergyDistributionAnalysis VEDA4 ProgramrdquoWarsaw Poland 2004ndash2010 httpwwwsmmgpl
[38] M H Jamroz J C Dobrowolski and R Brzozowski ldquoVibra-tional modes of 26- 27- and 23-diisopropylnaphthalene ADFT studyrdquo Journal of Molecular Structure vol 787 no 1ndash3 pp172ndash183 2006
[39] M H Jamroz ldquoVibrational Energy Distribution Analysis(VEDA) scopes and limitationsrdquo Spectrochimica Acta AMolec-ular and Biomolecular Spectroscopy vol 114 pp 220ndash230 2013
Journal of Chemistry 15
[40] R Marchal P Carbonniere D Begue and C Pouchan ldquoStruc-tural and vibrational determination of small galliumndasharsenideclusters fromCCSD(T) andDFT calculationsrdquoChemical PhysicsLetters vol 453 no 1ndash3 pp 49ndash54 2008
[41] R Marchal P Carbonniere and C Pouchan ldquoStructural andvibrational properties prediction of Sn
119899Te119899clusters (n = 2ndash
8) using the GSAM approachrdquo Computational and TheoreticalChemistry vol 990 pp 100ndash105 2012
[42] T Helgaker M Jaszunski and M Pecul ldquoThe quantum-chemical calculation of NMR indirect spin-spin coupling con-stantsrdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 53 no 4 pp 249ndash268 2008
[43] F A Perras andD L Bryce ldquoTheoretical study of homonuclear Jcoupling between quadrupolar spins single-crystal DOR andJ-resolved NMRrdquo Journal of Magnetic Resonance vol 242 pp23ndash32 2014
[44] I D Burns A F Hill A J P White D J Williams and J DE T Wilton-Ely ldquoPolyazolyl chelate chemistry 61 bidentatecoordination of HB(pz)
3(pz = Pyrazol-1-yl) to ruthenium and
osmium crystal structure of [RuH(CO)(PPh3)2k2-HB(pz)
3]rdquo
Organometallics vol 17 no 8 pp 1552ndash1557 1998[45] M Al-Noaimi and M A AlDamen ldquoRuthenium complexes
incorporating azoimine and 120572-diamine based ligands synthe-sis crystal structure electrochemistry and DFT calculationrdquoInorganica Chimica Acta vol 387 pp 45ndash51 2012
[46] K Nakajima Y Ando H Mano and M Kojima ldquoPhotosub-stitution reactivity crystal structures and electrochemistry ofruthenium(II) (III) complexes containing tetradentate (O
2N2
S2N2 and P
2N2) Schiff base ligandsrdquo Inorganica Chimica Acta
vol 274 no 2 pp 184ndash191 1998[47] Z-L Lu K Eichele I Warad et al ldquoSupported organometal-
lic complexes XXXVIII [1] Bis(methoxyethyldimethlphos-phine)ruthenium(II) complexes as transfer hydrogenation cat-alystsrdquo Zeitschrift fur Anorganische und Allgemeine Chemie vol629 no 7-8 pp 1308ndash1315 2003
[48] R Gaur and L Mishra ldquoSynthesis and characterization ofRu(II)ndashDMSOndashClndashchalcone complexes DNA binding nucle-ase and topoisomerase II inhibitory activityrdquo Inorganic Chem-istry vol 51 no 5 pp 3059ndash3070 2012
[49] B Cebrian-Losantos E Reisner C R Kowol et al ldquoSynthesisand reactivity of the aquation product of the antitumor complextrans-[Ru IIICI
4(indazole)
2] minusrdquo Inorganic Chemistry vol 47 no
14 pp 6513ndash6523 2008[50] B T Rasley M Rapta and R J Kulawiec ldquoDiastereoselectivity
in enolate coordination in a new class of chiral rutheniumenolate complexesrdquo Organometallics vol 15 no 13 pp 2852ndash2854 1996
[51] S David R S Perkins F R Fronczek S Kasiri S S MandalandR S Srivastava ldquoSynthesis characterization and anticanceractivity of ruthenium-pyrazole complexesrdquo Journal of InorganicBiochemistry vol 111 pp 33ndash39 2012
[52] B Dutta E Solari S Gauthier R Scopelliti and K SeverinldquoRuthenium half-sandwich complexes with sterically demand-ing cyclopentadienyl ligandsrdquo Organometallics vol 26 no 19pp 4791ndash4799 2007
[53] G Turkoglu S Tampier F Strinitz F W Heinemann E Hub-ner and N Burzlaff ldquoRuthenium carbonyl complexes bearingbis(pyrazol-1-yl)carboxylato ligandsrdquo Organometallics vol 31no 6 pp 2166ndash2174 2012
[54] A K Renfrew A D Phillips E Tapavicza R ScopellitiU Rothlisberger and P J Dyson ldquoTuning the efficacy of
ruthenium(II)-arene (RAPTA) antitumor compounds with flu-orinated arene ligandsrdquo Organometallics vol 28 no 17 pp5061ndash5071 2009
[55] P M Jeffries R E Ellenwood and G S Girolami ldquoAnionicruthenium(II) alkyls with ancillary diene and dienyl ligandssynthesis and structures of [(12057821205782-C
7H8)RuMe
4]2minus and [(12057831205782-
C8H11)RuMe
3]2minusrdquo Inorganica Chimica Acta vol 361 no 1 pp
3165ndash3170 2008[56] B R James D Dolphin T W Leung F W B Einstein
and A C Willis ldquoPreparation and characterization of someruthenium(III) porphyrins including the crystal structure ofbromo(octaethylporphinato)(triphenylphosphine)ruthenium(III)rdquoCanadian Journal of Chemistry vol 62 no 7 pp 1238ndash12451984
[57] M Plois R Wolf W Hujo and S Grimme ldquoTowards reagentsfor bimetallic activation reactions polyhydride complexes withRu2H3 Ru2ZnH6 and Cu
2Ru2H6coresrdquo European Journal of
Inorganic Chemistry vol 2013 no 17 pp 3039ndash3048 2013[58] L Hintermann L Xiao A Labonne and U Englert
ldquo[CpRu(1205786-naphthalene)]PF6as precursor in complex synthesis
and catalysis with the cyclopentadienyl-ruthenium(II) cationrdquoOrganometallics vol 28 no 19 pp 5739ndash5748 2009
[59] I W Wyman K N Robertson T S Cameron J C SwartsandM A S Aquino ldquoSynthesis structure and electrochemistryof (ferrocene-2-propenoato-OO1015840)bis[12-bis(diphenylphosphi-no)ethane-PP1015840]ruthenium(II) hexafluorophosphaterdquo Inorgan-ica Chimica Acta vol 359 no 9 pp 3092ndash3096 2006
[60] C A Vock C Scolaro A D Phillips R Scopelliti G Sava andP J Dyson ldquoSynthesis characterization and in vitro evaluationof novel ruthenium(II) 1205786-arene imidazole complexesrdquo Journalof Medicinal Chemistry vol 49 no 18 pp 5552ndash5561 2006
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
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Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
8 Journal of Chemistry
Table10Th
ecorrelationwith
inthed
ifferentm
etho
dsused
incompu
tingthefi
rsth
yperpo
lariz
abilitie
s
MP2
aug-cc-pV
TZMP2
DGDZV
PMP2
SBK
JCVDZ
CCSD
DGDZV
PCC
SDSBK
JCVDZ
PBEDGDZV
PPB
ESB
KJCVDZ
B3LY
PDGDZV
PB3
LYPSB
KJCVDZ
MP2
-acc
100
100
100
004
014
019
030
024
010
MP2
-dv
100
100
100
minus001
010
020
029
022
009
MP2
-ecp
100
100
100
minus005
006
019
027
019
006
CCSD
-dv
004
minus001
minus005
100
095
031
062
075
075
CCSD
-ECP
014
010
006
095
100
045
081
092
091
PBE-dv
019
020
019
031
045
100
042
051
053
PBE-EC
P030
029
027
062
081
042
100
097
095
B3LY
P-dv
024
022
019
075
092
051
097
100
099
B3LY
P-EC
P010
009
006
075
091
053
095
099
100
Journal of Chemistry 9
200 300 400 500 600 700200 300 400 500 600 700
200 300 400 500 600 700200 300 400 500 600 700
200 300 400 500 600 700200 300 400 500 600 700
Ru-C-MP2Ru-C-CCSD
Ru-C-PBE0Ru-C-B3LYP
Ru-N-MP2Ru-N-CCSD
Ru-N-PBE0Ru-N-B3LYP
Ru-O-MP2Ru-O-CCSD
Ru-O-PBE0Ru-O-B3LYP
Ru-Cl-MP2Ru-Cl-CCSD
Ru-Cl-PBE0Ru-Cl-B3LYP
Ru-P-MP2Ru-P-CCSD
Ru-P-PBE0Ru-P-B3LYP
Ru-S-MP2Ru-S-CCSD
Ru-S-PBE0Ru-S-B3LYP
Figure 3 The IR vibrations of the six models computed using MP2 (black) CCSD (red) PBE (green) and B3LYP (blue)
10 Journal of Chemistry
Table11Th
eIRvibrations
oftheR
u-Lbo
ndsa
tdifferentcom
putatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
6077
72349120573(H
RuH)120592(Ru-C)
5872
73346120592(Ru-C)
68224
195
120592(Ru-C)
63297
226
120573(H
RuH)120592(Ru-C)
50222
238
120591(H
RuCH
)120592(Ru-C)
53062
71120573(H
RuH)120592(Ru-C)
Ru-N
71899
977
120592(Ru-N)120592(Ru-H)
62352
1636120592(Ru-N)
66265
2879120573(H
RuH)120592(Ru-N)
71495
1013
120592(Ru-N)
48235
101120592(Ru-N)
49539
738
120592(Ru-N)
65608
137
120573(H
RuH)120592(Ru-N)
Ru-O
7178
11371
120592(Ru-O)
63412
1586120592(Ru-O)
70574
75120592(Ru-O)
68889
2395
120592(Ru-O)
Ru-C
l43529
2195
120592(Ru-Cl)
5913
3644
120592(Ru-Cl)
65732
376
120592(Ru-Cl)
32331
1022
120592(Ru-Cl)
4478
43433
120592(Ru-Cl)
Ru-P
28203
171
120592(Ru-P)
2393
9395
120592(Ru-P)
44535
232
120592(Ru-P)
2793
71025
o(Ru
HPH
)120592(Ru-P)
23442
711
o(Ru
HPH
)120592(Ru-P)
Ru-S
4119
4401
120592(Ru-S)
32619
424
120592(Ru-S)
3574
92496
o(Ru
HSH
)120592(Ru-S)
40866
311
120592(Ru-S)
37311
597
o(Ru
HSH
)120592(Ru-S)
38596
1999
120592(Ru-S)
120592isstr
etching120573isbend
ing120591istorsionalandoisou
t-of-p
lane
torsional
Journal of Chemistry 11
Table12Th
eassignm
ento
fthe
prom
inentIRvibrations
ofthem
odels
atdifferent
compu
tatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
346783
9624120573(H
RuH)120592(Ru-H)
386628
124120573(H
RuH)120573(H
RuH)
120592(C
H)120592(Ru-H)
381759
1510
1120573(H
RuH)120573(H
RuH)
120591(H
RuHC)
30511
103120592(C
H)o(Ru
HCH
)120592(C
H)
313241
8772
120592(C
H)120592(C
H)
344585
6003
120592(Ru-H)
326534
582120573(H
CH)120592(C
H)120592(Ru-H)
3044
61
5191120592(C
H)o(Ru
HCH
)120592(Ru-H)
306501
5614120573(H
RuH)120573(H
RuH)
o(Ru
HCH
)323718
7402120573(H
CH)120573(H
RuH)120592(C
H)
310576
7913
120573(H
RuH)120592(Ru-H)
29104116677
120592(C
H)120592(C
H)
299873
14381
120592(C
H)120592(C
H)
310607
10481120573(H
RuC)
120591(H
CRuH
)o(Ru
HCH
)230969
6851120573(H
RuH)120591(H
RuHC)
120592(Ru-H)
247128
4498120573(H
RuH)o(Ru
HCH
)120592(Ru-H)
240085
1095
1120592(C
H)
231944
1014
7120573(H
RuC)
o(RuH
CH)
207553
969120573(H
RuH)120573(H
RuH)
120592(Ru-H)120592(Ru-H)
232314
1296
8120592(C
H)
Ru-N
38020714205120573(H
RuH)120573(H
RuH)
120573(H
RuH)
401043
1231120573(H
RuH)120591(H
RuHN)
120592(N
H)
403478
11428120591(H
RuNH)o(Ru
HNH)
120592(N
H)
353289
10673120573(H
RuH)120573(H
RuH)
339019
20019
120592(N
H)120592(N
H)
347897
18119120573(H
RuH)120573(H
RuH)
120591(H
RuHN)120592(Ru-H)
347497
1866120573(H
RuH)120573(H
RuH)
120592(Ru-H)
331504
19282
120592(N
H)120592(N
H)
32687139839
120592(N
H)120592(N
H)
336728
2897
5120592(Ru-H)
332695
1499
5120573(H
RuH)o(Ru
HNH)
318372
37524
120592(N
H)120592(N
H)
293151
4214120592(Ru-H)120592(Ru-H)120592(N
H)
120592(N
H)
327085
3514120573(H
RuH)120591(H
RuHN)
120592(Ru-H)
2746
17455
o(Ru
HNH)120592(Ru-H)
120592(Ru-H)
238961
4007120573(H
RuH)120592(Ru-H)
207916
6108
120592(Ru-H)
199979
4338
120573(H
NH)
210524
6443
o(Ru
HNH)120592(N
H)
120592(Ru-H)
203734
6557
120592(Ru-H)
Ru-O
372613
2694
9120592(O
H)
380749
28041
o(Ru
HOH)120592(Ru-H)
389061
1005
o(Ru
HOH)120573(H
RuH)
3608772399
3120592(O
H)
275932
1407120573(H
RuH)o(Ru
HOH)
o(Ru
HOH)120592(Ru-H)
31079
1921120573(H
RuO)120573(H
RuH)
o(Ru
HOH)
370979
51891120573(H
RuO)120573(H
RuO)
327956
2992120573(H
RuH)120573(H
RuH)
18598
2333
120592(Ru-H)120592(Ru-H)
179443
2374120573(H
RuH)o(Ru
HOH)
120592(Ru-H)
291506
5502
o(Ru
HOH)120592(Ru-H)
120592(Ru-H)
220079
1599120573(H
RuH)o(Ru
HOH)
120592(Ru-H)120592(Ru-H)
1346
08
2894120592(Ru-H)120592(Ru-H)
125632
2895120592(Ru-H)120573(H
ORu
)260461
4569120592(O
H)120573(H
ORu
)203014
1588
120592(Ru-H)
112741
9479120573(H
RuH)120592(Ru-H)
120592(Ru-H)
109235
7374
120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
205106
3383120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
147934
29120592(Ru-H)120592(Ru-H)
Ru-C
l185546
2458
120592(Ru-H)
308667
1411120573(H
RuH)o(Ru
HClH)
120592(Ru-H)
30365123653
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
22088
2242
120592(Ru-H)
131751
3288
120592(Ru-H)
179947
2511
o(Ru
HClH)120592(Ru-H)
120592(Ru-H)
261179
3015
120592(Ru-H)120573(H
RuH)
210816
1124
120592(Ru-H)
114581
9421
120592(Ru-H)
121159
3269120573(H
RuH)120573(H
RuH)
120573(H
RuCl)
20399
3006120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
203112
1687
120592(Ru-H)
84759
3157
120592(Ru-H)
110861
7222
o(Ru
HClH)o(Ru
HClH)
120592(Ru-H)120573(H
RuCl)
131224
3565
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
147293
3151
120592(Ru-H)
79488
381
120573(H
RuH)
7687
2483120573(H
RuH)120592(Ru-H)
120592(Ru-H)120592(Ru-H)
109164
1501120592(Ru-H)120573(H
RuH)
11346
9195
3120573(H
RuH)
12 Journal of Chemistry
Table12C
ontin
ued
B3LY
PCC
SDMP2
PBE
Ru-P
384575
1547
120573(H
RuH)
40856716207120573(H
RuH)120591(H
RuPH
)o(Ru
HPH
)410148
11361120573(H
RuH)120573(H
RuH)
3509879645120573(H
RuH)120592(Ru-H)
296363
1457120573(H
RuH)120592(Ru-H)
328227
1508120573(H
RuH)120573(H
RuH)
120591(H
PRuH
)264975
4273
120573(H
RuP)120592(Ru-H)
246259
4871
120592(PH)120592(PH)
253628
4006
120592(PH)120592(PH)
261721
3138
120592(Ru-H)
262336
4752
120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
24307
5689
120592(PH)120592(PH)
250603
4624
120592(PH)120592(PH)
259379
3579
120573(H
RuP)
256933
4865120573(H
RuP)120573
(HRu
H)
238468
1306120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
245899
7096
120592(PH)120592(PH)
255419
4427120573(H
RuH)120591(H
PRuH
)120591(H
PRuH
)228633
8692
120573(H
RuH)120592(PH)
237354
92120592(PH)
Ru-S
265041
1308
120592(SH)
290793
378120573(H
RuH)120591(H
SRuH
)120592(Ru-H)120573(H
RuS)
417199
15487
o(Ru
HSH
)o(Ru
HSH
)120573(H
RuH)
34606
2384120573(H
RuH)120573(H
RuH)
120573(H
RuH)o(Ru
HSH
)
26342
1916
120573(H
RuH)120592(Ru-H)
188073
1685120573(H
RuH)120573(H
RuH)
120592(Ru-H)
28041
199265120573(H
RuS)120573
(HRu
H)
120573(H
RuH)120592(Ru-H)
258225
1254
120592(SH)
1913
1699
120592(Ru-H)
114853
2967120591(H
SRuH
)120592(SH)
120592(Ru-H)
2385442392374
120573(H
RuS)
21675
2604
120592(Ru-H)
121642
3386120592(Ru-H)120592(Ru-H)
109859
10132120573(H
RuH)120591(H
SRuH
)o(Ru
HSH
)120592(Ru-H)
225761
44894
120592(Ru-H)120573(H
RuH)
132047
3699120592(Ru-H)120592(Ru-H)
11086
11006120573(H
RuH)120592(Ru-H)
82534
331120591(H
SRuH
)120592(Ru-H)
120592(Ru-H)
210643
5205
120592(Ru-H)
8835
5098
o(Ru
HSH
)o(Ru
HSH
)120592(Ru-H)120592(Ru-H)
Journal of Chemistry 13
all the methods Ru-C Ru-N and Ru-O vibrations are withinthe range of 500 to 720 which is far higher than the rangeof vibrations of Ru-Cl Ru-P and Ru-S which are foundwithin the range of 224 to 658 Generally the order of Ru-L vibrations can be assumed as Ru-N gt Ru-O gt Ru-C gtRu-Cl gt Ru-S gt Ru-P (Table 11) The wavenumbers of thevibrations computed from the different methods appear to besignificantly different from each other in values and positions(Figure 3) The features of the IR spectra using MP2 andCCSD are very similar in the models Some vibration around291506 in model Ru-O 303651 in Ru-Cl and 238544 inRu-S are very prominent in MP2 methods compared to inany other methods or even absent in other methods Forinstance the bending of the angle of HRuS which is found tobe prominent in MP2 method is completely absent in othermethods (see Figure 3 and Table 12) The MP2 and CCSDshow strong vibrations within the range of 3800 to 4100 inmany of the models which are obviously absent in manyof the PBE and B3LYP methods Using the PED methodas implemented in VEDA package most of these vibrationsat high frequencies are a result of the torsional and out-of-plane vibration of H-Ru-X-H where X represents the typeof the model as shown in Table 12 In addition most of thebending vibrations which are determined by PBE and B3LYPfrom 2800 to 3800 in the models are also determined byMP2 and CCSD though some cases are at lower wavenumbercompared to PBE and B3LYP (Table 12) In the models Ru-Oand Ru-Cl PBE and B3LYP give priority to the OH and RuHvibrations respectively whileMP2 andCCSD give priority tothe torsional stretching and angle bending of their atoms
4 Conclusions
Six models of Ru-L bonds Ru-C Ru-N Ru-O Ru-Cl Ru-P and Ru-S are built to represent common rutheniumcomplexes and possible ruthenium-receptor interactionsThe reproducibility of their geometrical electronic spec-troscopic and conductive properties was investigated usingMP2 CCSD PBE and B3LYP functionals with differentcombination of basis sets Generally we observed that thereproducibility of most of the properties is much easier usingdifferent basis sets compared to using different functionalmethods as a result of significant geometrical changes whichis possible especially if there are many light atoms likehydrogen atoms as in themodelsThe order of the energy andthe thermodynamic properties are found to be reproducibleusing different functionalmethods and basis sets butHOMOLUMO 119869-coupling hyperpolarizabilities and isotropic andanisotropic shielding are found to depend more on the typeof the functional used rather than on the type of the basis setThe only significant similarity observed among the methodsapplied in computing hyperpolarizabilities is that they allrated models Ru-S Ru-Cl and Ru-O among their best threeThe optimized geometries and the thermodynamic proper-ties obtained from the functional PBE are found to be verysimilar to MP2 and perform better than B3LYP and CCSDwhich further give insight into many literaturesrsquo preferencefor PBE in optimizing metal complexes In computation ofthe isotropic and anisotropic shielding tensors B3LYP gives
values similar to MP2 and performs better than PBE The IRvibrations and assignment clearly show that the vibrationsobtained from the MP2 and CCSD methods are very similarand give preference to the torsional and bending vibrationsof the molecules over their stretching The order of the IRvibrations of the ruthenium-ligand bonds can be assumed asRu-N gt Ru-O gt Ru-C gt Ru-Cl gt Ru-S gt Ru-P
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
The authors gracefully acknowledged the financial support ofGovan Mbeki Research and Development Centre Universityof Fort Hare South Africa The CHPC in Republic ofSouth Africa is gracefully acknowledged for providing thecomputing facilities and some of the software used for thecomputation
References
[1] B Dutta R Scopelliti and K Severin ldquoSynthesis structure andreactivity of the methoxy-bridged dimer [CpandRu(120583-OMe)]
2
(Cpand = 1205785-1-methoxy-24-di-tert-butyl-3-neopentylcyclopenta-dienyl)rdquo Organometallics vol 27 no 3 pp 423ndash429 2008
[2] M A Furrer F Schmitt M Wiederkehr L Juillerat-Jeanneretand B Therrien ldquoCellular delivery of pyrenyl-arene rutheniumcomplexes by a water-soluble arene ruthenium metalla-cagerdquoDalton Transactions vol 41 no 24 pp 7201ndash7211 2012
[3] Q ZhouW Lei YChen et al ldquoRuthenium(II)-arene complexeswith strong fluorescence insight into the underlying mecha-nismrdquoChemistrymdashA European Journal vol 18 no 28 pp 8617ndash8621 2012
[4] L Bıro E Farkas and P Buglyo ldquoHydrolytic behaviour andchloride ion binding capability of [Ru(1205786 minus119901minus cym)(H
2O)3]2+
a solution equilibrium studyrdquoDalton Transactions vol 41 no 1pp 285ndash291 2012
[5] Y Boutadla D L Davies R C Jones and K Singh ldquoThescope of ambiphilic acetate-assisted cyclometallation with half-sandwich complexes of iridium rhodium and rutheniumrdquoChemistrymdashA European Journal vol 17 no 12 pp 3438ndash34482011
[6] Y F Han H Li Y Fei Y J Lin W Z Zhang and GX Jin ldquoSynthesis and structural characterization of binuclearhalf-sandwich iridium rhodium and ruthenium complexescontaining 441015840-dipyridyldisulfide (4DPDS) ligandsrdquo DaltonTransactions vol 39 no 30 pp 7119ndash7124 2010
[7] B Dutta B F Curchod P Campomanes et al ldquoReactions ofalkynes with [RuCl(cyclopentadienyl)] complexes the impor-tant first stepsrdquo ChemistrymdashA European Journal vol 16 no 28pp 8400ndash8409 2010
[8] M Jimenez-Tenorio M C Puerta P Valerga S MonchoG Ujaque and A Lledos ldquoProton-transfer reactions to half-sandwich ruthenium trihydride complexes bearing hemilabilePN ligands experimental and density functional theory stud-iesrdquo Inorganic Chemistry vol 49 no 13 pp 6035ndash6057 2010
14 Journal of Chemistry
[9] B Dutta C Scolaro R Scopelliti P J Dyson and K Sev-erin ldquoImportance of the 120587-ligand remarkable effect of thecyclopentadienyl ring on the cytotoxicity of ruthenium PTAcompoundsrdquoOrganometallics vol 27 no 7 pp 1355ndash1357 2008
[10] T Bugarcic A Habtemariam J Stepankova et al ldquoThe con-trasting chemistry and cancer cell cytotoxicity of bipyridineand bipyridinediol ruthenium(II) arene complexesrdquo InorganicChemistry vol 47 no 24 pp 11470ndash11486 2008
[11] M Castellano-Castillo H Kostrhunova V Marini et al ldquoBind-ing ofmismatch repair proteinMutS tomispairedDNA adductsof intercalating ruthenium(II) arene complexesrdquo Journal ofBiological Inorganic Chemistry vol 13 no 6 pp 993ndash999 2008
[12] S J Dougan A Habtemariam S E McHale S Parsons andP J Sadler ldquoCatalytic organometallic anticancer complexesrdquoProceedings of the National Academy of Sciences of the UnitedStates of America vol 105 no 33 pp 11628ndash11633 2008
[13] S J Dougan M Melchart A Habtemariam S Parsons and PJ Sadler ldquoPhenylazo-pyridine and phenylazo-pyrazole chloridoruthenium(II) arene complexes arene loss aquation and can-cer cell cytotoxicityrdquo Inorganic Chemistry vol 45 no 26 pp10882ndash10894 2006
[14] V Ritleng P Bertani M Pfeffer C Sirlin and J HirschingerldquoOptically active ortho-metalated half-sandwich rutheniumcomplexes solid-state NMR as a convenient tool to analyzemixtures of diastereomersrdquo Inorganic Chemistry vol 40 no 20pp 5117ndash5122 2001
[15] Y Sunada Y Hayashi H Kawaguchi and K TatsumildquoAlkynethiolato and alkyneselenolato rutheniumhalf-sandwichcomplexes Synthesis structures and reactions with (1205785ndashC5H5)2Zrrdquo Inorganic Chemistry vol 40 no 27 pp 7072ndash70782001
[16] K Yamanari R Ito S Yamamoto et al ldquoCyclic tetramerscomposed of rhodium(III) iridium(III) or ruthenium(II) half-sandwich and6-purinethionesrdquo Inorganic Chemistry vol 41 no25 pp 6824ndash6830 2002
[17] F Caruso M Rossi A Benson et al ldquoRuthenium-arenecomplexes of curcumin X-ray and density functional the-ory structure synthesis and spectroscopic characterizationin vitro antitumor activity and DNA docking studies of (p-cymene)Ru(curcuminato)chlorordquo Journal of Medicinal Chem-istry vol 55 no 3 pp 1072ndash1081 2012
[18] C Gossens I Tavernelli and U Rothlisberger ldquoBinding oforganometallic ruthenium(II) anticancer compounds to nucle-obases a computational studyrdquo Journal of Physical Chemistry Avol 113 no 43 pp 11888ndash11897 2009
[19] A M Pizarro A Habtemariam and P J Sadler ldquoActiva-tion mechanisms for organometallic anticancer complexesrdquoin Medicinal Organometallic Chemistry vol 32 of Topics inOrganometallic Chemistry pp 21ndash56 Springer Berlin Ger-many 2010
[20] I Turel and J Kljun ldquoInteractions of metal ions with DNAits constituents and derivatives which may be relevant foranticancer researchrdquoCurrent Topics inMedicinal Chemistry vol11 no 21 pp 2661ndash2687 2011
[21] G Gasser I Ott and N Metzler-Nolte ldquoOrganometallic anti-cancer compoundsrdquo Journal of Medicinal Chemistry vol 54 no1 pp 3ndash25 2011
[22] K J Kilpin S Crot T Riedel J A Kitchen and P JDyson ldquoRuthenium(II) and osmium(II) 123-triazolylideneorganometallics a preliminary investigation into the biologicalactivity of rsquoclickrsquo carbene complexesrdquo Dalton Transactions vol43 no 3 pp 1443ndash1448 2014
[23] A F A Peacock S Parsons and P J Sadler ldquoTuning thehydrolytic aqueous chemistry of osmium arene complexeswith NO-chelating ligands to achieve cancer cell cytotoxicityrdquoJournal of the American Chemical Society vol 129 no 11 pp3348ndash3357 2007
[24] A F A Peacock M Melchart R J Deeth A Habtemariam SParsons and P J Sadler ldquoOsmium(II) and ruthenium(II) arenemaltolato complexes rapid hydrolysis and nucleobase bindingrdquoChemistrymdashA European Journal vol 13 no 9 pp 2601ndash26132007
[25] F Pelletier V Comte A Massard et al ldquoDevelopment ofbimetallic titanoceneminusrutheniumminusarene complexes as anti-cancer agents relationships between structural and biologicalpropertiesrdquo Journal of Medicinal Chemistry vol 53 no 19 pp6923ndash6933 2010
[26] K J Kilpin and P J Dyson ldquoEnzyme inhibition by metalcomplexes concepts strategies and applicationsrdquo ChemicalScience vol 4 no 4 pp 1410ndash1419 2013
[27] G Gasser andNMetzler-Nolte ldquoThe potential of organometal-lic complexes in medicinal chemistryrdquo Current Opinion inChemical Biology vol 16 no 1-2 pp 84ndash91 2012
[28] I Turel J Kljun F Perdih et al ldquoFirst ruthenium organometal-lic complex of antibacterial agent ofloxacin Crystal structureand interactions with DNArdquo Inorganic Chemistry vol 49 no23 pp 10750ndash10752 2010
[29] C Adamo and V Barone ldquoToward reliable density functionalmethods without adjustable parameters the PBE0 modelrdquoJournal of Chemical Physics vol 110 no 13 pp 6158ndash6170 1999
[30] A D Becke ldquoDensity-functional thermochemistry IIIThe roleof exact exchangerdquoThe Journal of Chemical Physics vol 98 no7 article 5648 1993
[31] W J Stevens M Krauss H Basch and P G Jasien ldquoRelativisticcompact effective potentials and efficient shared-exponentbasis sets for the third- fourth- and fifth-row atomsrdquoCanadianJournal of Chemistry vol 70 no 2 pp 612ndash630 1992
[32] M J Frisch GW Trucks H B Schlegel et alOfficial Gaussian09 Literature Citation Gaussian Wallingford UK 2009
[33] D J Feller ldquoThe role of databases in support of computationalchemistry calculationsrdquo Journal of Computational Chemistryvol 17 no 13 pp 1571ndash1586 1996
[34] K L Schuchardt B T Didier T Elsethagen et al ldquoBasis setexchange a community database for computational sciencesrdquoJournal of Chemical Information andModeling vol 47 no 3 pp1045ndash1052 2007
[35] Y Liu C-G Liu S-L Sun G-C Yang and Y-Q QiuldquoRedox-switching second-order nonlinear optical responses ofNandNandN ruthenium complexesrdquo Computational and TheoreticalChemistry vol 979 pp 112ndash118 2012
[36] P S Liyanage R M de Silva and K M N de Silva ldquoNonlinearoptical (NLO) properties of novel organometallic complexeshigh accuracy density functional theory (DFT) calculationsrdquoJournal of Molecular Structure THEOCHEM vol 639 pp 195ndash201 2003
[37] MH Jamroz ldquoVibrational EnergyDistributionAnalysis VEDA4 ProgramrdquoWarsaw Poland 2004ndash2010 httpwwwsmmgpl
[38] M H Jamroz J C Dobrowolski and R Brzozowski ldquoVibra-tional modes of 26- 27- and 23-diisopropylnaphthalene ADFT studyrdquo Journal of Molecular Structure vol 787 no 1ndash3 pp172ndash183 2006
[39] M H Jamroz ldquoVibrational Energy Distribution Analysis(VEDA) scopes and limitationsrdquo Spectrochimica Acta AMolec-ular and Biomolecular Spectroscopy vol 114 pp 220ndash230 2013
Journal of Chemistry 15
[40] R Marchal P Carbonniere D Begue and C Pouchan ldquoStruc-tural and vibrational determination of small galliumndasharsenideclusters fromCCSD(T) andDFT calculationsrdquoChemical PhysicsLetters vol 453 no 1ndash3 pp 49ndash54 2008
[41] R Marchal P Carbonniere and C Pouchan ldquoStructural andvibrational properties prediction of Sn
119899Te119899clusters (n = 2ndash
8) using the GSAM approachrdquo Computational and TheoreticalChemistry vol 990 pp 100ndash105 2012
[42] T Helgaker M Jaszunski and M Pecul ldquoThe quantum-chemical calculation of NMR indirect spin-spin coupling con-stantsrdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 53 no 4 pp 249ndash268 2008
[43] F A Perras andD L Bryce ldquoTheoretical study of homonuclear Jcoupling between quadrupolar spins single-crystal DOR andJ-resolved NMRrdquo Journal of Magnetic Resonance vol 242 pp23ndash32 2014
[44] I D Burns A F Hill A J P White D J Williams and J DE T Wilton-Ely ldquoPolyazolyl chelate chemistry 61 bidentatecoordination of HB(pz)
3(pz = Pyrazol-1-yl) to ruthenium and
osmium crystal structure of [RuH(CO)(PPh3)2k2-HB(pz)
3]rdquo
Organometallics vol 17 no 8 pp 1552ndash1557 1998[45] M Al-Noaimi and M A AlDamen ldquoRuthenium complexes
incorporating azoimine and 120572-diamine based ligands synthe-sis crystal structure electrochemistry and DFT calculationrdquoInorganica Chimica Acta vol 387 pp 45ndash51 2012
[46] K Nakajima Y Ando H Mano and M Kojima ldquoPhotosub-stitution reactivity crystal structures and electrochemistry ofruthenium(II) (III) complexes containing tetradentate (O
2N2
S2N2 and P
2N2) Schiff base ligandsrdquo Inorganica Chimica Acta
vol 274 no 2 pp 184ndash191 1998[47] Z-L Lu K Eichele I Warad et al ldquoSupported organometal-
lic complexes XXXVIII [1] Bis(methoxyethyldimethlphos-phine)ruthenium(II) complexes as transfer hydrogenation cat-alystsrdquo Zeitschrift fur Anorganische und Allgemeine Chemie vol629 no 7-8 pp 1308ndash1315 2003
[48] R Gaur and L Mishra ldquoSynthesis and characterization ofRu(II)ndashDMSOndashClndashchalcone complexes DNA binding nucle-ase and topoisomerase II inhibitory activityrdquo Inorganic Chem-istry vol 51 no 5 pp 3059ndash3070 2012
[49] B Cebrian-Losantos E Reisner C R Kowol et al ldquoSynthesisand reactivity of the aquation product of the antitumor complextrans-[Ru IIICI
4(indazole)
2] minusrdquo Inorganic Chemistry vol 47 no
14 pp 6513ndash6523 2008[50] B T Rasley M Rapta and R J Kulawiec ldquoDiastereoselectivity
in enolate coordination in a new class of chiral rutheniumenolate complexesrdquo Organometallics vol 15 no 13 pp 2852ndash2854 1996
[51] S David R S Perkins F R Fronczek S Kasiri S S MandalandR S Srivastava ldquoSynthesis characterization and anticanceractivity of ruthenium-pyrazole complexesrdquo Journal of InorganicBiochemistry vol 111 pp 33ndash39 2012
[52] B Dutta E Solari S Gauthier R Scopelliti and K SeverinldquoRuthenium half-sandwich complexes with sterically demand-ing cyclopentadienyl ligandsrdquo Organometallics vol 26 no 19pp 4791ndash4799 2007
[53] G Turkoglu S Tampier F Strinitz F W Heinemann E Hub-ner and N Burzlaff ldquoRuthenium carbonyl complexes bearingbis(pyrazol-1-yl)carboxylato ligandsrdquo Organometallics vol 31no 6 pp 2166ndash2174 2012
[54] A K Renfrew A D Phillips E Tapavicza R ScopellitiU Rothlisberger and P J Dyson ldquoTuning the efficacy of
ruthenium(II)-arene (RAPTA) antitumor compounds with flu-orinated arene ligandsrdquo Organometallics vol 28 no 17 pp5061ndash5071 2009
[55] P M Jeffries R E Ellenwood and G S Girolami ldquoAnionicruthenium(II) alkyls with ancillary diene and dienyl ligandssynthesis and structures of [(12057821205782-C
7H8)RuMe
4]2minus and [(12057831205782-
C8H11)RuMe
3]2minusrdquo Inorganica Chimica Acta vol 361 no 1 pp
3165ndash3170 2008[56] B R James D Dolphin T W Leung F W B Einstein
and A C Willis ldquoPreparation and characterization of someruthenium(III) porphyrins including the crystal structure ofbromo(octaethylporphinato)(triphenylphosphine)ruthenium(III)rdquoCanadian Journal of Chemistry vol 62 no 7 pp 1238ndash12451984
[57] M Plois R Wolf W Hujo and S Grimme ldquoTowards reagentsfor bimetallic activation reactions polyhydride complexes withRu2H3 Ru2ZnH6 and Cu
2Ru2H6coresrdquo European Journal of
Inorganic Chemistry vol 2013 no 17 pp 3039ndash3048 2013[58] L Hintermann L Xiao A Labonne and U Englert
ldquo[CpRu(1205786-naphthalene)]PF6as precursor in complex synthesis
and catalysis with the cyclopentadienyl-ruthenium(II) cationrdquoOrganometallics vol 28 no 19 pp 5739ndash5748 2009
[59] I W Wyman K N Robertson T S Cameron J C SwartsandM A S Aquino ldquoSynthesis structure and electrochemistryof (ferrocene-2-propenoato-OO1015840)bis[12-bis(diphenylphosphi-no)ethane-PP1015840]ruthenium(II) hexafluorophosphaterdquo Inorgan-ica Chimica Acta vol 359 no 9 pp 3092ndash3096 2006
[60] C A Vock C Scolaro A D Phillips R Scopelliti G Sava andP J Dyson ldquoSynthesis characterization and in vitro evaluationof novel ruthenium(II) 1205786-arene imidazole complexesrdquo Journalof Medicinal Chemistry vol 49 no 18 pp 5552ndash5561 2006
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Analytical Methods in Chemistry
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Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Journal of
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Analytical ChemistryInternational Journal of
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Organic Chemistry International
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CatalystsJournal of
Journal of Chemistry 9
200 300 400 500 600 700200 300 400 500 600 700
200 300 400 500 600 700200 300 400 500 600 700
200 300 400 500 600 700200 300 400 500 600 700
Ru-C-MP2Ru-C-CCSD
Ru-C-PBE0Ru-C-B3LYP
Ru-N-MP2Ru-N-CCSD
Ru-N-PBE0Ru-N-B3LYP
Ru-O-MP2Ru-O-CCSD
Ru-O-PBE0Ru-O-B3LYP
Ru-Cl-MP2Ru-Cl-CCSD
Ru-Cl-PBE0Ru-Cl-B3LYP
Ru-P-MP2Ru-P-CCSD
Ru-P-PBE0Ru-P-B3LYP
Ru-S-MP2Ru-S-CCSD
Ru-S-PBE0Ru-S-B3LYP
Figure 3 The IR vibrations of the six models computed using MP2 (black) CCSD (red) PBE (green) and B3LYP (blue)
10 Journal of Chemistry
Table11Th
eIRvibrations
oftheR
u-Lbo
ndsa
tdifferentcom
putatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
6077
72349120573(H
RuH)120592(Ru-C)
5872
73346120592(Ru-C)
68224
195
120592(Ru-C)
63297
226
120573(H
RuH)120592(Ru-C)
50222
238
120591(H
RuCH
)120592(Ru-C)
53062
71120573(H
RuH)120592(Ru-C)
Ru-N
71899
977
120592(Ru-N)120592(Ru-H)
62352
1636120592(Ru-N)
66265
2879120573(H
RuH)120592(Ru-N)
71495
1013
120592(Ru-N)
48235
101120592(Ru-N)
49539
738
120592(Ru-N)
65608
137
120573(H
RuH)120592(Ru-N)
Ru-O
7178
11371
120592(Ru-O)
63412
1586120592(Ru-O)
70574
75120592(Ru-O)
68889
2395
120592(Ru-O)
Ru-C
l43529
2195
120592(Ru-Cl)
5913
3644
120592(Ru-Cl)
65732
376
120592(Ru-Cl)
32331
1022
120592(Ru-Cl)
4478
43433
120592(Ru-Cl)
Ru-P
28203
171
120592(Ru-P)
2393
9395
120592(Ru-P)
44535
232
120592(Ru-P)
2793
71025
o(Ru
HPH
)120592(Ru-P)
23442
711
o(Ru
HPH
)120592(Ru-P)
Ru-S
4119
4401
120592(Ru-S)
32619
424
120592(Ru-S)
3574
92496
o(Ru
HSH
)120592(Ru-S)
40866
311
120592(Ru-S)
37311
597
o(Ru
HSH
)120592(Ru-S)
38596
1999
120592(Ru-S)
120592isstr
etching120573isbend
ing120591istorsionalandoisou
t-of-p
lane
torsional
Journal of Chemistry 11
Table12Th
eassignm
ento
fthe
prom
inentIRvibrations
ofthem
odels
atdifferent
compu
tatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
346783
9624120573(H
RuH)120592(Ru-H)
386628
124120573(H
RuH)120573(H
RuH)
120592(C
H)120592(Ru-H)
381759
1510
1120573(H
RuH)120573(H
RuH)
120591(H
RuHC)
30511
103120592(C
H)o(Ru
HCH
)120592(C
H)
313241
8772
120592(C
H)120592(C
H)
344585
6003
120592(Ru-H)
326534
582120573(H
CH)120592(C
H)120592(Ru-H)
3044
61
5191120592(C
H)o(Ru
HCH
)120592(Ru-H)
306501
5614120573(H
RuH)120573(H
RuH)
o(Ru
HCH
)323718
7402120573(H
CH)120573(H
RuH)120592(C
H)
310576
7913
120573(H
RuH)120592(Ru-H)
29104116677
120592(C
H)120592(C
H)
299873
14381
120592(C
H)120592(C
H)
310607
10481120573(H
RuC)
120591(H
CRuH
)o(Ru
HCH
)230969
6851120573(H
RuH)120591(H
RuHC)
120592(Ru-H)
247128
4498120573(H
RuH)o(Ru
HCH
)120592(Ru-H)
240085
1095
1120592(C
H)
231944
1014
7120573(H
RuC)
o(RuH
CH)
207553
969120573(H
RuH)120573(H
RuH)
120592(Ru-H)120592(Ru-H)
232314
1296
8120592(C
H)
Ru-N
38020714205120573(H
RuH)120573(H
RuH)
120573(H
RuH)
401043
1231120573(H
RuH)120591(H
RuHN)
120592(N
H)
403478
11428120591(H
RuNH)o(Ru
HNH)
120592(N
H)
353289
10673120573(H
RuH)120573(H
RuH)
339019
20019
120592(N
H)120592(N
H)
347897
18119120573(H
RuH)120573(H
RuH)
120591(H
RuHN)120592(Ru-H)
347497
1866120573(H
RuH)120573(H
RuH)
120592(Ru-H)
331504
19282
120592(N
H)120592(N
H)
32687139839
120592(N
H)120592(N
H)
336728
2897
5120592(Ru-H)
332695
1499
5120573(H
RuH)o(Ru
HNH)
318372
37524
120592(N
H)120592(N
H)
293151
4214120592(Ru-H)120592(Ru-H)120592(N
H)
120592(N
H)
327085
3514120573(H
RuH)120591(H
RuHN)
120592(Ru-H)
2746
17455
o(Ru
HNH)120592(Ru-H)
120592(Ru-H)
238961
4007120573(H
RuH)120592(Ru-H)
207916
6108
120592(Ru-H)
199979
4338
120573(H
NH)
210524
6443
o(Ru
HNH)120592(N
H)
120592(Ru-H)
203734
6557
120592(Ru-H)
Ru-O
372613
2694
9120592(O
H)
380749
28041
o(Ru
HOH)120592(Ru-H)
389061
1005
o(Ru
HOH)120573(H
RuH)
3608772399
3120592(O
H)
275932
1407120573(H
RuH)o(Ru
HOH)
o(Ru
HOH)120592(Ru-H)
31079
1921120573(H
RuO)120573(H
RuH)
o(Ru
HOH)
370979
51891120573(H
RuO)120573(H
RuO)
327956
2992120573(H
RuH)120573(H
RuH)
18598
2333
120592(Ru-H)120592(Ru-H)
179443
2374120573(H
RuH)o(Ru
HOH)
120592(Ru-H)
291506
5502
o(Ru
HOH)120592(Ru-H)
120592(Ru-H)
220079
1599120573(H
RuH)o(Ru
HOH)
120592(Ru-H)120592(Ru-H)
1346
08
2894120592(Ru-H)120592(Ru-H)
125632
2895120592(Ru-H)120573(H
ORu
)260461
4569120592(O
H)120573(H
ORu
)203014
1588
120592(Ru-H)
112741
9479120573(H
RuH)120592(Ru-H)
120592(Ru-H)
109235
7374
120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
205106
3383120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
147934
29120592(Ru-H)120592(Ru-H)
Ru-C
l185546
2458
120592(Ru-H)
308667
1411120573(H
RuH)o(Ru
HClH)
120592(Ru-H)
30365123653
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
22088
2242
120592(Ru-H)
131751
3288
120592(Ru-H)
179947
2511
o(Ru
HClH)120592(Ru-H)
120592(Ru-H)
261179
3015
120592(Ru-H)120573(H
RuH)
210816
1124
120592(Ru-H)
114581
9421
120592(Ru-H)
121159
3269120573(H
RuH)120573(H
RuH)
120573(H
RuCl)
20399
3006120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
203112
1687
120592(Ru-H)
84759
3157
120592(Ru-H)
110861
7222
o(Ru
HClH)o(Ru
HClH)
120592(Ru-H)120573(H
RuCl)
131224
3565
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
147293
3151
120592(Ru-H)
79488
381
120573(H
RuH)
7687
2483120573(H
RuH)120592(Ru-H)
120592(Ru-H)120592(Ru-H)
109164
1501120592(Ru-H)120573(H
RuH)
11346
9195
3120573(H
RuH)
12 Journal of Chemistry
Table12C
ontin
ued
B3LY
PCC
SDMP2
PBE
Ru-P
384575
1547
120573(H
RuH)
40856716207120573(H
RuH)120591(H
RuPH
)o(Ru
HPH
)410148
11361120573(H
RuH)120573(H
RuH)
3509879645120573(H
RuH)120592(Ru-H)
296363
1457120573(H
RuH)120592(Ru-H)
328227
1508120573(H
RuH)120573(H
RuH)
120591(H
PRuH
)264975
4273
120573(H
RuP)120592(Ru-H)
246259
4871
120592(PH)120592(PH)
253628
4006
120592(PH)120592(PH)
261721
3138
120592(Ru-H)
262336
4752
120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
24307
5689
120592(PH)120592(PH)
250603
4624
120592(PH)120592(PH)
259379
3579
120573(H
RuP)
256933
4865120573(H
RuP)120573
(HRu
H)
238468
1306120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
245899
7096
120592(PH)120592(PH)
255419
4427120573(H
RuH)120591(H
PRuH
)120591(H
PRuH
)228633
8692
120573(H
RuH)120592(PH)
237354
92120592(PH)
Ru-S
265041
1308
120592(SH)
290793
378120573(H
RuH)120591(H
SRuH
)120592(Ru-H)120573(H
RuS)
417199
15487
o(Ru
HSH
)o(Ru
HSH
)120573(H
RuH)
34606
2384120573(H
RuH)120573(H
RuH)
120573(H
RuH)o(Ru
HSH
)
26342
1916
120573(H
RuH)120592(Ru-H)
188073
1685120573(H
RuH)120573(H
RuH)
120592(Ru-H)
28041
199265120573(H
RuS)120573
(HRu
H)
120573(H
RuH)120592(Ru-H)
258225
1254
120592(SH)
1913
1699
120592(Ru-H)
114853
2967120591(H
SRuH
)120592(SH)
120592(Ru-H)
2385442392374
120573(H
RuS)
21675
2604
120592(Ru-H)
121642
3386120592(Ru-H)120592(Ru-H)
109859
10132120573(H
RuH)120591(H
SRuH
)o(Ru
HSH
)120592(Ru-H)
225761
44894
120592(Ru-H)120573(H
RuH)
132047
3699120592(Ru-H)120592(Ru-H)
11086
11006120573(H
RuH)120592(Ru-H)
82534
331120591(H
SRuH
)120592(Ru-H)
120592(Ru-H)
210643
5205
120592(Ru-H)
8835
5098
o(Ru
HSH
)o(Ru
HSH
)120592(Ru-H)120592(Ru-H)
Journal of Chemistry 13
all the methods Ru-C Ru-N and Ru-O vibrations are withinthe range of 500 to 720 which is far higher than the rangeof vibrations of Ru-Cl Ru-P and Ru-S which are foundwithin the range of 224 to 658 Generally the order of Ru-L vibrations can be assumed as Ru-N gt Ru-O gt Ru-C gtRu-Cl gt Ru-S gt Ru-P (Table 11) The wavenumbers of thevibrations computed from the different methods appear to besignificantly different from each other in values and positions(Figure 3) The features of the IR spectra using MP2 andCCSD are very similar in the models Some vibration around291506 in model Ru-O 303651 in Ru-Cl and 238544 inRu-S are very prominent in MP2 methods compared to inany other methods or even absent in other methods Forinstance the bending of the angle of HRuS which is found tobe prominent in MP2 method is completely absent in othermethods (see Figure 3 and Table 12) The MP2 and CCSDshow strong vibrations within the range of 3800 to 4100 inmany of the models which are obviously absent in manyof the PBE and B3LYP methods Using the PED methodas implemented in VEDA package most of these vibrationsat high frequencies are a result of the torsional and out-of-plane vibration of H-Ru-X-H where X represents the typeof the model as shown in Table 12 In addition most of thebending vibrations which are determined by PBE and B3LYPfrom 2800 to 3800 in the models are also determined byMP2 and CCSD though some cases are at lower wavenumbercompared to PBE and B3LYP (Table 12) In the models Ru-Oand Ru-Cl PBE and B3LYP give priority to the OH and RuHvibrations respectively whileMP2 andCCSD give priority tothe torsional stretching and angle bending of their atoms
4 Conclusions
Six models of Ru-L bonds Ru-C Ru-N Ru-O Ru-Cl Ru-P and Ru-S are built to represent common rutheniumcomplexes and possible ruthenium-receptor interactionsThe reproducibility of their geometrical electronic spec-troscopic and conductive properties was investigated usingMP2 CCSD PBE and B3LYP functionals with differentcombination of basis sets Generally we observed that thereproducibility of most of the properties is much easier usingdifferent basis sets compared to using different functionalmethods as a result of significant geometrical changes whichis possible especially if there are many light atoms likehydrogen atoms as in themodelsThe order of the energy andthe thermodynamic properties are found to be reproducibleusing different functionalmethods and basis sets butHOMOLUMO 119869-coupling hyperpolarizabilities and isotropic andanisotropic shielding are found to depend more on the typeof the functional used rather than on the type of the basis setThe only significant similarity observed among the methodsapplied in computing hyperpolarizabilities is that they allrated models Ru-S Ru-Cl and Ru-O among their best threeThe optimized geometries and the thermodynamic proper-ties obtained from the functional PBE are found to be verysimilar to MP2 and perform better than B3LYP and CCSDwhich further give insight into many literaturesrsquo preferencefor PBE in optimizing metal complexes In computation ofthe isotropic and anisotropic shielding tensors B3LYP gives
values similar to MP2 and performs better than PBE The IRvibrations and assignment clearly show that the vibrationsobtained from the MP2 and CCSD methods are very similarand give preference to the torsional and bending vibrationsof the molecules over their stretching The order of the IRvibrations of the ruthenium-ligand bonds can be assumed asRu-N gt Ru-O gt Ru-C gt Ru-Cl gt Ru-S gt Ru-P
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
The authors gracefully acknowledged the financial support ofGovan Mbeki Research and Development Centre Universityof Fort Hare South Africa The CHPC in Republic ofSouth Africa is gracefully acknowledged for providing thecomputing facilities and some of the software used for thecomputation
References
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2
(Cpand = 1205785-1-methoxy-24-di-tert-butyl-3-neopentylcyclopenta-dienyl)rdquo Organometallics vol 27 no 3 pp 423ndash429 2008
[2] M A Furrer F Schmitt M Wiederkehr L Juillerat-Jeanneretand B Therrien ldquoCellular delivery of pyrenyl-arene rutheniumcomplexes by a water-soluble arene ruthenium metalla-cagerdquoDalton Transactions vol 41 no 24 pp 7201ndash7211 2012
[3] Q ZhouW Lei YChen et al ldquoRuthenium(II)-arene complexeswith strong fluorescence insight into the underlying mecha-nismrdquoChemistrymdashA European Journal vol 18 no 28 pp 8617ndash8621 2012
[4] L Bıro E Farkas and P Buglyo ldquoHydrolytic behaviour andchloride ion binding capability of [Ru(1205786 minus119901minus cym)(H
2O)3]2+
a solution equilibrium studyrdquoDalton Transactions vol 41 no 1pp 285ndash291 2012
[5] Y Boutadla D L Davies R C Jones and K Singh ldquoThescope of ambiphilic acetate-assisted cyclometallation with half-sandwich complexes of iridium rhodium and rutheniumrdquoChemistrymdashA European Journal vol 17 no 12 pp 3438ndash34482011
[6] Y F Han H Li Y Fei Y J Lin W Z Zhang and GX Jin ldquoSynthesis and structural characterization of binuclearhalf-sandwich iridium rhodium and ruthenium complexescontaining 441015840-dipyridyldisulfide (4DPDS) ligandsrdquo DaltonTransactions vol 39 no 30 pp 7119ndash7124 2010
[7] B Dutta B F Curchod P Campomanes et al ldquoReactions ofalkynes with [RuCl(cyclopentadienyl)] complexes the impor-tant first stepsrdquo ChemistrymdashA European Journal vol 16 no 28pp 8400ndash8409 2010
[8] M Jimenez-Tenorio M C Puerta P Valerga S MonchoG Ujaque and A Lledos ldquoProton-transfer reactions to half-sandwich ruthenium trihydride complexes bearing hemilabilePN ligands experimental and density functional theory stud-iesrdquo Inorganic Chemistry vol 49 no 13 pp 6035ndash6057 2010
14 Journal of Chemistry
[9] B Dutta C Scolaro R Scopelliti P J Dyson and K Sev-erin ldquoImportance of the 120587-ligand remarkable effect of thecyclopentadienyl ring on the cytotoxicity of ruthenium PTAcompoundsrdquoOrganometallics vol 27 no 7 pp 1355ndash1357 2008
[10] T Bugarcic A Habtemariam J Stepankova et al ldquoThe con-trasting chemistry and cancer cell cytotoxicity of bipyridineand bipyridinediol ruthenium(II) arene complexesrdquo InorganicChemistry vol 47 no 24 pp 11470ndash11486 2008
[11] M Castellano-Castillo H Kostrhunova V Marini et al ldquoBind-ing ofmismatch repair proteinMutS tomispairedDNA adductsof intercalating ruthenium(II) arene complexesrdquo Journal ofBiological Inorganic Chemistry vol 13 no 6 pp 993ndash999 2008
[12] S J Dougan A Habtemariam S E McHale S Parsons andP J Sadler ldquoCatalytic organometallic anticancer complexesrdquoProceedings of the National Academy of Sciences of the UnitedStates of America vol 105 no 33 pp 11628ndash11633 2008
[13] S J Dougan M Melchart A Habtemariam S Parsons and PJ Sadler ldquoPhenylazo-pyridine and phenylazo-pyrazole chloridoruthenium(II) arene complexes arene loss aquation and can-cer cell cytotoxicityrdquo Inorganic Chemistry vol 45 no 26 pp10882ndash10894 2006
[14] V Ritleng P Bertani M Pfeffer C Sirlin and J HirschingerldquoOptically active ortho-metalated half-sandwich rutheniumcomplexes solid-state NMR as a convenient tool to analyzemixtures of diastereomersrdquo Inorganic Chemistry vol 40 no 20pp 5117ndash5122 2001
[15] Y Sunada Y Hayashi H Kawaguchi and K TatsumildquoAlkynethiolato and alkyneselenolato rutheniumhalf-sandwichcomplexes Synthesis structures and reactions with (1205785ndashC5H5)2Zrrdquo Inorganic Chemistry vol 40 no 27 pp 7072ndash70782001
[16] K Yamanari R Ito S Yamamoto et al ldquoCyclic tetramerscomposed of rhodium(III) iridium(III) or ruthenium(II) half-sandwich and6-purinethionesrdquo Inorganic Chemistry vol 41 no25 pp 6824ndash6830 2002
[17] F Caruso M Rossi A Benson et al ldquoRuthenium-arenecomplexes of curcumin X-ray and density functional the-ory structure synthesis and spectroscopic characterizationin vitro antitumor activity and DNA docking studies of (p-cymene)Ru(curcuminato)chlorordquo Journal of Medicinal Chem-istry vol 55 no 3 pp 1072ndash1081 2012
[18] C Gossens I Tavernelli and U Rothlisberger ldquoBinding oforganometallic ruthenium(II) anticancer compounds to nucle-obases a computational studyrdquo Journal of Physical Chemistry Avol 113 no 43 pp 11888ndash11897 2009
[19] A M Pizarro A Habtemariam and P J Sadler ldquoActiva-tion mechanisms for organometallic anticancer complexesrdquoin Medicinal Organometallic Chemistry vol 32 of Topics inOrganometallic Chemistry pp 21ndash56 Springer Berlin Ger-many 2010
[20] I Turel and J Kljun ldquoInteractions of metal ions with DNAits constituents and derivatives which may be relevant foranticancer researchrdquoCurrent Topics inMedicinal Chemistry vol11 no 21 pp 2661ndash2687 2011
[21] G Gasser I Ott and N Metzler-Nolte ldquoOrganometallic anti-cancer compoundsrdquo Journal of Medicinal Chemistry vol 54 no1 pp 3ndash25 2011
[22] K J Kilpin S Crot T Riedel J A Kitchen and P JDyson ldquoRuthenium(II) and osmium(II) 123-triazolylideneorganometallics a preliminary investigation into the biologicalactivity of rsquoclickrsquo carbene complexesrdquo Dalton Transactions vol43 no 3 pp 1443ndash1448 2014
[23] A F A Peacock S Parsons and P J Sadler ldquoTuning thehydrolytic aqueous chemistry of osmium arene complexeswith NO-chelating ligands to achieve cancer cell cytotoxicityrdquoJournal of the American Chemical Society vol 129 no 11 pp3348ndash3357 2007
[24] A F A Peacock M Melchart R J Deeth A Habtemariam SParsons and P J Sadler ldquoOsmium(II) and ruthenium(II) arenemaltolato complexes rapid hydrolysis and nucleobase bindingrdquoChemistrymdashA European Journal vol 13 no 9 pp 2601ndash26132007
[25] F Pelletier V Comte A Massard et al ldquoDevelopment ofbimetallic titanoceneminusrutheniumminusarene complexes as anti-cancer agents relationships between structural and biologicalpropertiesrdquo Journal of Medicinal Chemistry vol 53 no 19 pp6923ndash6933 2010
[26] K J Kilpin and P J Dyson ldquoEnzyme inhibition by metalcomplexes concepts strategies and applicationsrdquo ChemicalScience vol 4 no 4 pp 1410ndash1419 2013
[27] G Gasser andNMetzler-Nolte ldquoThe potential of organometal-lic complexes in medicinal chemistryrdquo Current Opinion inChemical Biology vol 16 no 1-2 pp 84ndash91 2012
[28] I Turel J Kljun F Perdih et al ldquoFirst ruthenium organometal-lic complex of antibacterial agent ofloxacin Crystal structureand interactions with DNArdquo Inorganic Chemistry vol 49 no23 pp 10750ndash10752 2010
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[31] W J Stevens M Krauss H Basch and P G Jasien ldquoRelativisticcompact effective potentials and efficient shared-exponentbasis sets for the third- fourth- and fifth-row atomsrdquoCanadianJournal of Chemistry vol 70 no 2 pp 612ndash630 1992
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[33] D J Feller ldquoThe role of databases in support of computationalchemistry calculationsrdquo Journal of Computational Chemistryvol 17 no 13 pp 1571ndash1586 1996
[34] K L Schuchardt B T Didier T Elsethagen et al ldquoBasis setexchange a community database for computational sciencesrdquoJournal of Chemical Information andModeling vol 47 no 3 pp1045ndash1052 2007
[35] Y Liu C-G Liu S-L Sun G-C Yang and Y-Q QiuldquoRedox-switching second-order nonlinear optical responses ofNandNandN ruthenium complexesrdquo Computational and TheoreticalChemistry vol 979 pp 112ndash118 2012
[36] P S Liyanage R M de Silva and K M N de Silva ldquoNonlinearoptical (NLO) properties of novel organometallic complexeshigh accuracy density functional theory (DFT) calculationsrdquoJournal of Molecular Structure THEOCHEM vol 639 pp 195ndash201 2003
[37] MH Jamroz ldquoVibrational EnergyDistributionAnalysis VEDA4 ProgramrdquoWarsaw Poland 2004ndash2010 httpwwwsmmgpl
[38] M H Jamroz J C Dobrowolski and R Brzozowski ldquoVibra-tional modes of 26- 27- and 23-diisopropylnaphthalene ADFT studyrdquo Journal of Molecular Structure vol 787 no 1ndash3 pp172ndash183 2006
[39] M H Jamroz ldquoVibrational Energy Distribution Analysis(VEDA) scopes and limitationsrdquo Spectrochimica Acta AMolec-ular and Biomolecular Spectroscopy vol 114 pp 220ndash230 2013
Journal of Chemistry 15
[40] R Marchal P Carbonniere D Begue and C Pouchan ldquoStruc-tural and vibrational determination of small galliumndasharsenideclusters fromCCSD(T) andDFT calculationsrdquoChemical PhysicsLetters vol 453 no 1ndash3 pp 49ndash54 2008
[41] R Marchal P Carbonniere and C Pouchan ldquoStructural andvibrational properties prediction of Sn
119899Te119899clusters (n = 2ndash
8) using the GSAM approachrdquo Computational and TheoreticalChemistry vol 990 pp 100ndash105 2012
[42] T Helgaker M Jaszunski and M Pecul ldquoThe quantum-chemical calculation of NMR indirect spin-spin coupling con-stantsrdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 53 no 4 pp 249ndash268 2008
[43] F A Perras andD L Bryce ldquoTheoretical study of homonuclear Jcoupling between quadrupolar spins single-crystal DOR andJ-resolved NMRrdquo Journal of Magnetic Resonance vol 242 pp23ndash32 2014
[44] I D Burns A F Hill A J P White D J Williams and J DE T Wilton-Ely ldquoPolyazolyl chelate chemistry 61 bidentatecoordination of HB(pz)
3(pz = Pyrazol-1-yl) to ruthenium and
osmium crystal structure of [RuH(CO)(PPh3)2k2-HB(pz)
3]rdquo
Organometallics vol 17 no 8 pp 1552ndash1557 1998[45] M Al-Noaimi and M A AlDamen ldquoRuthenium complexes
incorporating azoimine and 120572-diamine based ligands synthe-sis crystal structure electrochemistry and DFT calculationrdquoInorganica Chimica Acta vol 387 pp 45ndash51 2012
[46] K Nakajima Y Ando H Mano and M Kojima ldquoPhotosub-stitution reactivity crystal structures and electrochemistry ofruthenium(II) (III) complexes containing tetradentate (O
2N2
S2N2 and P
2N2) Schiff base ligandsrdquo Inorganica Chimica Acta
vol 274 no 2 pp 184ndash191 1998[47] Z-L Lu K Eichele I Warad et al ldquoSupported organometal-
lic complexes XXXVIII [1] Bis(methoxyethyldimethlphos-phine)ruthenium(II) complexes as transfer hydrogenation cat-alystsrdquo Zeitschrift fur Anorganische und Allgemeine Chemie vol629 no 7-8 pp 1308ndash1315 2003
[48] R Gaur and L Mishra ldquoSynthesis and characterization ofRu(II)ndashDMSOndashClndashchalcone complexes DNA binding nucle-ase and topoisomerase II inhibitory activityrdquo Inorganic Chem-istry vol 51 no 5 pp 3059ndash3070 2012
[49] B Cebrian-Losantos E Reisner C R Kowol et al ldquoSynthesisand reactivity of the aquation product of the antitumor complextrans-[Ru IIICI
4(indazole)
2] minusrdquo Inorganic Chemistry vol 47 no
14 pp 6513ndash6523 2008[50] B T Rasley M Rapta and R J Kulawiec ldquoDiastereoselectivity
in enolate coordination in a new class of chiral rutheniumenolate complexesrdquo Organometallics vol 15 no 13 pp 2852ndash2854 1996
[51] S David R S Perkins F R Fronczek S Kasiri S S MandalandR S Srivastava ldquoSynthesis characterization and anticanceractivity of ruthenium-pyrazole complexesrdquo Journal of InorganicBiochemistry vol 111 pp 33ndash39 2012
[52] B Dutta E Solari S Gauthier R Scopelliti and K SeverinldquoRuthenium half-sandwich complexes with sterically demand-ing cyclopentadienyl ligandsrdquo Organometallics vol 26 no 19pp 4791ndash4799 2007
[53] G Turkoglu S Tampier F Strinitz F W Heinemann E Hub-ner and N Burzlaff ldquoRuthenium carbonyl complexes bearingbis(pyrazol-1-yl)carboxylato ligandsrdquo Organometallics vol 31no 6 pp 2166ndash2174 2012
[54] A K Renfrew A D Phillips E Tapavicza R ScopellitiU Rothlisberger and P J Dyson ldquoTuning the efficacy of
ruthenium(II)-arene (RAPTA) antitumor compounds with flu-orinated arene ligandsrdquo Organometallics vol 28 no 17 pp5061ndash5071 2009
[55] P M Jeffries R E Ellenwood and G S Girolami ldquoAnionicruthenium(II) alkyls with ancillary diene and dienyl ligandssynthesis and structures of [(12057821205782-C
7H8)RuMe
4]2minus and [(12057831205782-
C8H11)RuMe
3]2minusrdquo Inorganica Chimica Acta vol 361 no 1 pp
3165ndash3170 2008[56] B R James D Dolphin T W Leung F W B Einstein
and A C Willis ldquoPreparation and characterization of someruthenium(III) porphyrins including the crystal structure ofbromo(octaethylporphinato)(triphenylphosphine)ruthenium(III)rdquoCanadian Journal of Chemistry vol 62 no 7 pp 1238ndash12451984
[57] M Plois R Wolf W Hujo and S Grimme ldquoTowards reagentsfor bimetallic activation reactions polyhydride complexes withRu2H3 Ru2ZnH6 and Cu
2Ru2H6coresrdquo European Journal of
Inorganic Chemistry vol 2013 no 17 pp 3039ndash3048 2013[58] L Hintermann L Xiao A Labonne and U Englert
ldquo[CpRu(1205786-naphthalene)]PF6as precursor in complex synthesis
and catalysis with the cyclopentadienyl-ruthenium(II) cationrdquoOrganometallics vol 28 no 19 pp 5739ndash5748 2009
[59] I W Wyman K N Robertson T S Cameron J C SwartsandM A S Aquino ldquoSynthesis structure and electrochemistryof (ferrocene-2-propenoato-OO1015840)bis[12-bis(diphenylphosphi-no)ethane-PP1015840]ruthenium(II) hexafluorophosphaterdquo Inorgan-ica Chimica Acta vol 359 no 9 pp 3092ndash3096 2006
[60] C A Vock C Scolaro A D Phillips R Scopelliti G Sava andP J Dyson ldquoSynthesis characterization and in vitro evaluationof novel ruthenium(II) 1205786-arene imidazole complexesrdquo Journalof Medicinal Chemistry vol 49 no 18 pp 5552ndash5561 2006
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CatalystsJournal of
10 Journal of Chemistry
Table11Th
eIRvibrations
oftheR
u-Lbo
ndsa
tdifferentcom
putatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
6077
72349120573(H
RuH)120592(Ru-C)
5872
73346120592(Ru-C)
68224
195
120592(Ru-C)
63297
226
120573(H
RuH)120592(Ru-C)
50222
238
120591(H
RuCH
)120592(Ru-C)
53062
71120573(H
RuH)120592(Ru-C)
Ru-N
71899
977
120592(Ru-N)120592(Ru-H)
62352
1636120592(Ru-N)
66265
2879120573(H
RuH)120592(Ru-N)
71495
1013
120592(Ru-N)
48235
101120592(Ru-N)
49539
738
120592(Ru-N)
65608
137
120573(H
RuH)120592(Ru-N)
Ru-O
7178
11371
120592(Ru-O)
63412
1586120592(Ru-O)
70574
75120592(Ru-O)
68889
2395
120592(Ru-O)
Ru-C
l43529
2195
120592(Ru-Cl)
5913
3644
120592(Ru-Cl)
65732
376
120592(Ru-Cl)
32331
1022
120592(Ru-Cl)
4478
43433
120592(Ru-Cl)
Ru-P
28203
171
120592(Ru-P)
2393
9395
120592(Ru-P)
44535
232
120592(Ru-P)
2793
71025
o(Ru
HPH
)120592(Ru-P)
23442
711
o(Ru
HPH
)120592(Ru-P)
Ru-S
4119
4401
120592(Ru-S)
32619
424
120592(Ru-S)
3574
92496
o(Ru
HSH
)120592(Ru-S)
40866
311
120592(Ru-S)
37311
597
o(Ru
HSH
)120592(Ru-S)
38596
1999
120592(Ru-S)
120592isstr
etching120573isbend
ing120591istorsionalandoisou
t-of-p
lane
torsional
Journal of Chemistry 11
Table12Th
eassignm
ento
fthe
prom
inentIRvibrations
ofthem
odels
atdifferent
compu
tatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
346783
9624120573(H
RuH)120592(Ru-H)
386628
124120573(H
RuH)120573(H
RuH)
120592(C
H)120592(Ru-H)
381759
1510
1120573(H
RuH)120573(H
RuH)
120591(H
RuHC)
30511
103120592(C
H)o(Ru
HCH
)120592(C
H)
313241
8772
120592(C
H)120592(C
H)
344585
6003
120592(Ru-H)
326534
582120573(H
CH)120592(C
H)120592(Ru-H)
3044
61
5191120592(C
H)o(Ru
HCH
)120592(Ru-H)
306501
5614120573(H
RuH)120573(H
RuH)
o(Ru
HCH
)323718
7402120573(H
CH)120573(H
RuH)120592(C
H)
310576
7913
120573(H
RuH)120592(Ru-H)
29104116677
120592(C
H)120592(C
H)
299873
14381
120592(C
H)120592(C
H)
310607
10481120573(H
RuC)
120591(H
CRuH
)o(Ru
HCH
)230969
6851120573(H
RuH)120591(H
RuHC)
120592(Ru-H)
247128
4498120573(H
RuH)o(Ru
HCH
)120592(Ru-H)
240085
1095
1120592(C
H)
231944
1014
7120573(H
RuC)
o(RuH
CH)
207553
969120573(H
RuH)120573(H
RuH)
120592(Ru-H)120592(Ru-H)
232314
1296
8120592(C
H)
Ru-N
38020714205120573(H
RuH)120573(H
RuH)
120573(H
RuH)
401043
1231120573(H
RuH)120591(H
RuHN)
120592(N
H)
403478
11428120591(H
RuNH)o(Ru
HNH)
120592(N
H)
353289
10673120573(H
RuH)120573(H
RuH)
339019
20019
120592(N
H)120592(N
H)
347897
18119120573(H
RuH)120573(H
RuH)
120591(H
RuHN)120592(Ru-H)
347497
1866120573(H
RuH)120573(H
RuH)
120592(Ru-H)
331504
19282
120592(N
H)120592(N
H)
32687139839
120592(N
H)120592(N
H)
336728
2897
5120592(Ru-H)
332695
1499
5120573(H
RuH)o(Ru
HNH)
318372
37524
120592(N
H)120592(N
H)
293151
4214120592(Ru-H)120592(Ru-H)120592(N
H)
120592(N
H)
327085
3514120573(H
RuH)120591(H
RuHN)
120592(Ru-H)
2746
17455
o(Ru
HNH)120592(Ru-H)
120592(Ru-H)
238961
4007120573(H
RuH)120592(Ru-H)
207916
6108
120592(Ru-H)
199979
4338
120573(H
NH)
210524
6443
o(Ru
HNH)120592(N
H)
120592(Ru-H)
203734
6557
120592(Ru-H)
Ru-O
372613
2694
9120592(O
H)
380749
28041
o(Ru
HOH)120592(Ru-H)
389061
1005
o(Ru
HOH)120573(H
RuH)
3608772399
3120592(O
H)
275932
1407120573(H
RuH)o(Ru
HOH)
o(Ru
HOH)120592(Ru-H)
31079
1921120573(H
RuO)120573(H
RuH)
o(Ru
HOH)
370979
51891120573(H
RuO)120573(H
RuO)
327956
2992120573(H
RuH)120573(H
RuH)
18598
2333
120592(Ru-H)120592(Ru-H)
179443
2374120573(H
RuH)o(Ru
HOH)
120592(Ru-H)
291506
5502
o(Ru
HOH)120592(Ru-H)
120592(Ru-H)
220079
1599120573(H
RuH)o(Ru
HOH)
120592(Ru-H)120592(Ru-H)
1346
08
2894120592(Ru-H)120592(Ru-H)
125632
2895120592(Ru-H)120573(H
ORu
)260461
4569120592(O
H)120573(H
ORu
)203014
1588
120592(Ru-H)
112741
9479120573(H
RuH)120592(Ru-H)
120592(Ru-H)
109235
7374
120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
205106
3383120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
147934
29120592(Ru-H)120592(Ru-H)
Ru-C
l185546
2458
120592(Ru-H)
308667
1411120573(H
RuH)o(Ru
HClH)
120592(Ru-H)
30365123653
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
22088
2242
120592(Ru-H)
131751
3288
120592(Ru-H)
179947
2511
o(Ru
HClH)120592(Ru-H)
120592(Ru-H)
261179
3015
120592(Ru-H)120573(H
RuH)
210816
1124
120592(Ru-H)
114581
9421
120592(Ru-H)
121159
3269120573(H
RuH)120573(H
RuH)
120573(H
RuCl)
20399
3006120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
203112
1687
120592(Ru-H)
84759
3157
120592(Ru-H)
110861
7222
o(Ru
HClH)o(Ru
HClH)
120592(Ru-H)120573(H
RuCl)
131224
3565
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
147293
3151
120592(Ru-H)
79488
381
120573(H
RuH)
7687
2483120573(H
RuH)120592(Ru-H)
120592(Ru-H)120592(Ru-H)
109164
1501120592(Ru-H)120573(H
RuH)
11346
9195
3120573(H
RuH)
12 Journal of Chemistry
Table12C
ontin
ued
B3LY
PCC
SDMP2
PBE
Ru-P
384575
1547
120573(H
RuH)
40856716207120573(H
RuH)120591(H
RuPH
)o(Ru
HPH
)410148
11361120573(H
RuH)120573(H
RuH)
3509879645120573(H
RuH)120592(Ru-H)
296363
1457120573(H
RuH)120592(Ru-H)
328227
1508120573(H
RuH)120573(H
RuH)
120591(H
PRuH
)264975
4273
120573(H
RuP)120592(Ru-H)
246259
4871
120592(PH)120592(PH)
253628
4006
120592(PH)120592(PH)
261721
3138
120592(Ru-H)
262336
4752
120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
24307
5689
120592(PH)120592(PH)
250603
4624
120592(PH)120592(PH)
259379
3579
120573(H
RuP)
256933
4865120573(H
RuP)120573
(HRu
H)
238468
1306120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
245899
7096
120592(PH)120592(PH)
255419
4427120573(H
RuH)120591(H
PRuH
)120591(H
PRuH
)228633
8692
120573(H
RuH)120592(PH)
237354
92120592(PH)
Ru-S
265041
1308
120592(SH)
290793
378120573(H
RuH)120591(H
SRuH
)120592(Ru-H)120573(H
RuS)
417199
15487
o(Ru
HSH
)o(Ru
HSH
)120573(H
RuH)
34606
2384120573(H
RuH)120573(H
RuH)
120573(H
RuH)o(Ru
HSH
)
26342
1916
120573(H
RuH)120592(Ru-H)
188073
1685120573(H
RuH)120573(H
RuH)
120592(Ru-H)
28041
199265120573(H
RuS)120573
(HRu
H)
120573(H
RuH)120592(Ru-H)
258225
1254
120592(SH)
1913
1699
120592(Ru-H)
114853
2967120591(H
SRuH
)120592(SH)
120592(Ru-H)
2385442392374
120573(H
RuS)
21675
2604
120592(Ru-H)
121642
3386120592(Ru-H)120592(Ru-H)
109859
10132120573(H
RuH)120591(H
SRuH
)o(Ru
HSH
)120592(Ru-H)
225761
44894
120592(Ru-H)120573(H
RuH)
132047
3699120592(Ru-H)120592(Ru-H)
11086
11006120573(H
RuH)120592(Ru-H)
82534
331120591(H
SRuH
)120592(Ru-H)
120592(Ru-H)
210643
5205
120592(Ru-H)
8835
5098
o(Ru
HSH
)o(Ru
HSH
)120592(Ru-H)120592(Ru-H)
Journal of Chemistry 13
all the methods Ru-C Ru-N and Ru-O vibrations are withinthe range of 500 to 720 which is far higher than the rangeof vibrations of Ru-Cl Ru-P and Ru-S which are foundwithin the range of 224 to 658 Generally the order of Ru-L vibrations can be assumed as Ru-N gt Ru-O gt Ru-C gtRu-Cl gt Ru-S gt Ru-P (Table 11) The wavenumbers of thevibrations computed from the different methods appear to besignificantly different from each other in values and positions(Figure 3) The features of the IR spectra using MP2 andCCSD are very similar in the models Some vibration around291506 in model Ru-O 303651 in Ru-Cl and 238544 inRu-S are very prominent in MP2 methods compared to inany other methods or even absent in other methods Forinstance the bending of the angle of HRuS which is found tobe prominent in MP2 method is completely absent in othermethods (see Figure 3 and Table 12) The MP2 and CCSDshow strong vibrations within the range of 3800 to 4100 inmany of the models which are obviously absent in manyof the PBE and B3LYP methods Using the PED methodas implemented in VEDA package most of these vibrationsat high frequencies are a result of the torsional and out-of-plane vibration of H-Ru-X-H where X represents the typeof the model as shown in Table 12 In addition most of thebending vibrations which are determined by PBE and B3LYPfrom 2800 to 3800 in the models are also determined byMP2 and CCSD though some cases are at lower wavenumbercompared to PBE and B3LYP (Table 12) In the models Ru-Oand Ru-Cl PBE and B3LYP give priority to the OH and RuHvibrations respectively whileMP2 andCCSD give priority tothe torsional stretching and angle bending of their atoms
4 Conclusions
Six models of Ru-L bonds Ru-C Ru-N Ru-O Ru-Cl Ru-P and Ru-S are built to represent common rutheniumcomplexes and possible ruthenium-receptor interactionsThe reproducibility of their geometrical electronic spec-troscopic and conductive properties was investigated usingMP2 CCSD PBE and B3LYP functionals with differentcombination of basis sets Generally we observed that thereproducibility of most of the properties is much easier usingdifferent basis sets compared to using different functionalmethods as a result of significant geometrical changes whichis possible especially if there are many light atoms likehydrogen atoms as in themodelsThe order of the energy andthe thermodynamic properties are found to be reproducibleusing different functionalmethods and basis sets butHOMOLUMO 119869-coupling hyperpolarizabilities and isotropic andanisotropic shielding are found to depend more on the typeof the functional used rather than on the type of the basis setThe only significant similarity observed among the methodsapplied in computing hyperpolarizabilities is that they allrated models Ru-S Ru-Cl and Ru-O among their best threeThe optimized geometries and the thermodynamic proper-ties obtained from the functional PBE are found to be verysimilar to MP2 and perform better than B3LYP and CCSDwhich further give insight into many literaturesrsquo preferencefor PBE in optimizing metal complexes In computation ofthe isotropic and anisotropic shielding tensors B3LYP gives
values similar to MP2 and performs better than PBE The IRvibrations and assignment clearly show that the vibrationsobtained from the MP2 and CCSD methods are very similarand give preference to the torsional and bending vibrationsof the molecules over their stretching The order of the IRvibrations of the ruthenium-ligand bonds can be assumed asRu-N gt Ru-O gt Ru-C gt Ru-Cl gt Ru-S gt Ru-P
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
The authors gracefully acknowledged the financial support ofGovan Mbeki Research and Development Centre Universityof Fort Hare South Africa The CHPC in Republic ofSouth Africa is gracefully acknowledged for providing thecomputing facilities and some of the software used for thecomputation
References
[1] B Dutta R Scopelliti and K Severin ldquoSynthesis structure andreactivity of the methoxy-bridged dimer [CpandRu(120583-OMe)]
2
(Cpand = 1205785-1-methoxy-24-di-tert-butyl-3-neopentylcyclopenta-dienyl)rdquo Organometallics vol 27 no 3 pp 423ndash429 2008
[2] M A Furrer F Schmitt M Wiederkehr L Juillerat-Jeanneretand B Therrien ldquoCellular delivery of pyrenyl-arene rutheniumcomplexes by a water-soluble arene ruthenium metalla-cagerdquoDalton Transactions vol 41 no 24 pp 7201ndash7211 2012
[3] Q ZhouW Lei YChen et al ldquoRuthenium(II)-arene complexeswith strong fluorescence insight into the underlying mecha-nismrdquoChemistrymdashA European Journal vol 18 no 28 pp 8617ndash8621 2012
[4] L Bıro E Farkas and P Buglyo ldquoHydrolytic behaviour andchloride ion binding capability of [Ru(1205786 minus119901minus cym)(H
2O)3]2+
a solution equilibrium studyrdquoDalton Transactions vol 41 no 1pp 285ndash291 2012
[5] Y Boutadla D L Davies R C Jones and K Singh ldquoThescope of ambiphilic acetate-assisted cyclometallation with half-sandwich complexes of iridium rhodium and rutheniumrdquoChemistrymdashA European Journal vol 17 no 12 pp 3438ndash34482011
[6] Y F Han H Li Y Fei Y J Lin W Z Zhang and GX Jin ldquoSynthesis and structural characterization of binuclearhalf-sandwich iridium rhodium and ruthenium complexescontaining 441015840-dipyridyldisulfide (4DPDS) ligandsrdquo DaltonTransactions vol 39 no 30 pp 7119ndash7124 2010
[7] B Dutta B F Curchod P Campomanes et al ldquoReactions ofalkynes with [RuCl(cyclopentadienyl)] complexes the impor-tant first stepsrdquo ChemistrymdashA European Journal vol 16 no 28pp 8400ndash8409 2010
[8] M Jimenez-Tenorio M C Puerta P Valerga S MonchoG Ujaque and A Lledos ldquoProton-transfer reactions to half-sandwich ruthenium trihydride complexes bearing hemilabilePN ligands experimental and density functional theory stud-iesrdquo Inorganic Chemistry vol 49 no 13 pp 6035ndash6057 2010
14 Journal of Chemistry
[9] B Dutta C Scolaro R Scopelliti P J Dyson and K Sev-erin ldquoImportance of the 120587-ligand remarkable effect of thecyclopentadienyl ring on the cytotoxicity of ruthenium PTAcompoundsrdquoOrganometallics vol 27 no 7 pp 1355ndash1357 2008
[10] T Bugarcic A Habtemariam J Stepankova et al ldquoThe con-trasting chemistry and cancer cell cytotoxicity of bipyridineand bipyridinediol ruthenium(II) arene complexesrdquo InorganicChemistry vol 47 no 24 pp 11470ndash11486 2008
[11] M Castellano-Castillo H Kostrhunova V Marini et al ldquoBind-ing ofmismatch repair proteinMutS tomispairedDNA adductsof intercalating ruthenium(II) arene complexesrdquo Journal ofBiological Inorganic Chemistry vol 13 no 6 pp 993ndash999 2008
[12] S J Dougan A Habtemariam S E McHale S Parsons andP J Sadler ldquoCatalytic organometallic anticancer complexesrdquoProceedings of the National Academy of Sciences of the UnitedStates of America vol 105 no 33 pp 11628ndash11633 2008
[13] S J Dougan M Melchart A Habtemariam S Parsons and PJ Sadler ldquoPhenylazo-pyridine and phenylazo-pyrazole chloridoruthenium(II) arene complexes arene loss aquation and can-cer cell cytotoxicityrdquo Inorganic Chemistry vol 45 no 26 pp10882ndash10894 2006
[14] V Ritleng P Bertani M Pfeffer C Sirlin and J HirschingerldquoOptically active ortho-metalated half-sandwich rutheniumcomplexes solid-state NMR as a convenient tool to analyzemixtures of diastereomersrdquo Inorganic Chemistry vol 40 no 20pp 5117ndash5122 2001
[15] Y Sunada Y Hayashi H Kawaguchi and K TatsumildquoAlkynethiolato and alkyneselenolato rutheniumhalf-sandwichcomplexes Synthesis structures and reactions with (1205785ndashC5H5)2Zrrdquo Inorganic Chemistry vol 40 no 27 pp 7072ndash70782001
[16] K Yamanari R Ito S Yamamoto et al ldquoCyclic tetramerscomposed of rhodium(III) iridium(III) or ruthenium(II) half-sandwich and6-purinethionesrdquo Inorganic Chemistry vol 41 no25 pp 6824ndash6830 2002
[17] F Caruso M Rossi A Benson et al ldquoRuthenium-arenecomplexes of curcumin X-ray and density functional the-ory structure synthesis and spectroscopic characterizationin vitro antitumor activity and DNA docking studies of (p-cymene)Ru(curcuminato)chlorordquo Journal of Medicinal Chem-istry vol 55 no 3 pp 1072ndash1081 2012
[18] C Gossens I Tavernelli and U Rothlisberger ldquoBinding oforganometallic ruthenium(II) anticancer compounds to nucle-obases a computational studyrdquo Journal of Physical Chemistry Avol 113 no 43 pp 11888ndash11897 2009
[19] A M Pizarro A Habtemariam and P J Sadler ldquoActiva-tion mechanisms for organometallic anticancer complexesrdquoin Medicinal Organometallic Chemistry vol 32 of Topics inOrganometallic Chemistry pp 21ndash56 Springer Berlin Ger-many 2010
[20] I Turel and J Kljun ldquoInteractions of metal ions with DNAits constituents and derivatives which may be relevant foranticancer researchrdquoCurrent Topics inMedicinal Chemistry vol11 no 21 pp 2661ndash2687 2011
[21] G Gasser I Ott and N Metzler-Nolte ldquoOrganometallic anti-cancer compoundsrdquo Journal of Medicinal Chemistry vol 54 no1 pp 3ndash25 2011
[22] K J Kilpin S Crot T Riedel J A Kitchen and P JDyson ldquoRuthenium(II) and osmium(II) 123-triazolylideneorganometallics a preliminary investigation into the biologicalactivity of rsquoclickrsquo carbene complexesrdquo Dalton Transactions vol43 no 3 pp 1443ndash1448 2014
[23] A F A Peacock S Parsons and P J Sadler ldquoTuning thehydrolytic aqueous chemistry of osmium arene complexeswith NO-chelating ligands to achieve cancer cell cytotoxicityrdquoJournal of the American Chemical Society vol 129 no 11 pp3348ndash3357 2007
[24] A F A Peacock M Melchart R J Deeth A Habtemariam SParsons and P J Sadler ldquoOsmium(II) and ruthenium(II) arenemaltolato complexes rapid hydrolysis and nucleobase bindingrdquoChemistrymdashA European Journal vol 13 no 9 pp 2601ndash26132007
[25] F Pelletier V Comte A Massard et al ldquoDevelopment ofbimetallic titanoceneminusrutheniumminusarene complexes as anti-cancer agents relationships between structural and biologicalpropertiesrdquo Journal of Medicinal Chemistry vol 53 no 19 pp6923ndash6933 2010
[26] K J Kilpin and P J Dyson ldquoEnzyme inhibition by metalcomplexes concepts strategies and applicationsrdquo ChemicalScience vol 4 no 4 pp 1410ndash1419 2013
[27] G Gasser andNMetzler-Nolte ldquoThe potential of organometal-lic complexes in medicinal chemistryrdquo Current Opinion inChemical Biology vol 16 no 1-2 pp 84ndash91 2012
[28] I Turel J Kljun F Perdih et al ldquoFirst ruthenium organometal-lic complex of antibacterial agent ofloxacin Crystal structureand interactions with DNArdquo Inorganic Chemistry vol 49 no23 pp 10750ndash10752 2010
[29] C Adamo and V Barone ldquoToward reliable density functionalmethods without adjustable parameters the PBE0 modelrdquoJournal of Chemical Physics vol 110 no 13 pp 6158ndash6170 1999
[30] A D Becke ldquoDensity-functional thermochemistry IIIThe roleof exact exchangerdquoThe Journal of Chemical Physics vol 98 no7 article 5648 1993
[31] W J Stevens M Krauss H Basch and P G Jasien ldquoRelativisticcompact effective potentials and efficient shared-exponentbasis sets for the third- fourth- and fifth-row atomsrdquoCanadianJournal of Chemistry vol 70 no 2 pp 612ndash630 1992
[32] M J Frisch GW Trucks H B Schlegel et alOfficial Gaussian09 Literature Citation Gaussian Wallingford UK 2009
[33] D J Feller ldquoThe role of databases in support of computationalchemistry calculationsrdquo Journal of Computational Chemistryvol 17 no 13 pp 1571ndash1586 1996
[34] K L Schuchardt B T Didier T Elsethagen et al ldquoBasis setexchange a community database for computational sciencesrdquoJournal of Chemical Information andModeling vol 47 no 3 pp1045ndash1052 2007
[35] Y Liu C-G Liu S-L Sun G-C Yang and Y-Q QiuldquoRedox-switching second-order nonlinear optical responses ofNandNandN ruthenium complexesrdquo Computational and TheoreticalChemistry vol 979 pp 112ndash118 2012
[36] P S Liyanage R M de Silva and K M N de Silva ldquoNonlinearoptical (NLO) properties of novel organometallic complexeshigh accuracy density functional theory (DFT) calculationsrdquoJournal of Molecular Structure THEOCHEM vol 639 pp 195ndash201 2003
[37] MH Jamroz ldquoVibrational EnergyDistributionAnalysis VEDA4 ProgramrdquoWarsaw Poland 2004ndash2010 httpwwwsmmgpl
[38] M H Jamroz J C Dobrowolski and R Brzozowski ldquoVibra-tional modes of 26- 27- and 23-diisopropylnaphthalene ADFT studyrdquo Journal of Molecular Structure vol 787 no 1ndash3 pp172ndash183 2006
[39] M H Jamroz ldquoVibrational Energy Distribution Analysis(VEDA) scopes and limitationsrdquo Spectrochimica Acta AMolec-ular and Biomolecular Spectroscopy vol 114 pp 220ndash230 2013
Journal of Chemistry 15
[40] R Marchal P Carbonniere D Begue and C Pouchan ldquoStruc-tural and vibrational determination of small galliumndasharsenideclusters fromCCSD(T) andDFT calculationsrdquoChemical PhysicsLetters vol 453 no 1ndash3 pp 49ndash54 2008
[41] R Marchal P Carbonniere and C Pouchan ldquoStructural andvibrational properties prediction of Sn
119899Te119899clusters (n = 2ndash
8) using the GSAM approachrdquo Computational and TheoreticalChemistry vol 990 pp 100ndash105 2012
[42] T Helgaker M Jaszunski and M Pecul ldquoThe quantum-chemical calculation of NMR indirect spin-spin coupling con-stantsrdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 53 no 4 pp 249ndash268 2008
[43] F A Perras andD L Bryce ldquoTheoretical study of homonuclear Jcoupling between quadrupolar spins single-crystal DOR andJ-resolved NMRrdquo Journal of Magnetic Resonance vol 242 pp23ndash32 2014
[44] I D Burns A F Hill A J P White D J Williams and J DE T Wilton-Ely ldquoPolyazolyl chelate chemistry 61 bidentatecoordination of HB(pz)
3(pz = Pyrazol-1-yl) to ruthenium and
osmium crystal structure of [RuH(CO)(PPh3)2k2-HB(pz)
3]rdquo
Organometallics vol 17 no 8 pp 1552ndash1557 1998[45] M Al-Noaimi and M A AlDamen ldquoRuthenium complexes
incorporating azoimine and 120572-diamine based ligands synthe-sis crystal structure electrochemistry and DFT calculationrdquoInorganica Chimica Acta vol 387 pp 45ndash51 2012
[46] K Nakajima Y Ando H Mano and M Kojima ldquoPhotosub-stitution reactivity crystal structures and electrochemistry ofruthenium(II) (III) complexes containing tetradentate (O
2N2
S2N2 and P
2N2) Schiff base ligandsrdquo Inorganica Chimica Acta
vol 274 no 2 pp 184ndash191 1998[47] Z-L Lu K Eichele I Warad et al ldquoSupported organometal-
lic complexes XXXVIII [1] Bis(methoxyethyldimethlphos-phine)ruthenium(II) complexes as transfer hydrogenation cat-alystsrdquo Zeitschrift fur Anorganische und Allgemeine Chemie vol629 no 7-8 pp 1308ndash1315 2003
[48] R Gaur and L Mishra ldquoSynthesis and characterization ofRu(II)ndashDMSOndashClndashchalcone complexes DNA binding nucle-ase and topoisomerase II inhibitory activityrdquo Inorganic Chem-istry vol 51 no 5 pp 3059ndash3070 2012
[49] B Cebrian-Losantos E Reisner C R Kowol et al ldquoSynthesisand reactivity of the aquation product of the antitumor complextrans-[Ru IIICI
4(indazole)
2] minusrdquo Inorganic Chemistry vol 47 no
14 pp 6513ndash6523 2008[50] B T Rasley M Rapta and R J Kulawiec ldquoDiastereoselectivity
in enolate coordination in a new class of chiral rutheniumenolate complexesrdquo Organometallics vol 15 no 13 pp 2852ndash2854 1996
[51] S David R S Perkins F R Fronczek S Kasiri S S MandalandR S Srivastava ldquoSynthesis characterization and anticanceractivity of ruthenium-pyrazole complexesrdquo Journal of InorganicBiochemistry vol 111 pp 33ndash39 2012
[52] B Dutta E Solari S Gauthier R Scopelliti and K SeverinldquoRuthenium half-sandwich complexes with sterically demand-ing cyclopentadienyl ligandsrdquo Organometallics vol 26 no 19pp 4791ndash4799 2007
[53] G Turkoglu S Tampier F Strinitz F W Heinemann E Hub-ner and N Burzlaff ldquoRuthenium carbonyl complexes bearingbis(pyrazol-1-yl)carboxylato ligandsrdquo Organometallics vol 31no 6 pp 2166ndash2174 2012
[54] A K Renfrew A D Phillips E Tapavicza R ScopellitiU Rothlisberger and P J Dyson ldquoTuning the efficacy of
ruthenium(II)-arene (RAPTA) antitumor compounds with flu-orinated arene ligandsrdquo Organometallics vol 28 no 17 pp5061ndash5071 2009
[55] P M Jeffries R E Ellenwood and G S Girolami ldquoAnionicruthenium(II) alkyls with ancillary diene and dienyl ligandssynthesis and structures of [(12057821205782-C
7H8)RuMe
4]2minus and [(12057831205782-
C8H11)RuMe
3]2minusrdquo Inorganica Chimica Acta vol 361 no 1 pp
3165ndash3170 2008[56] B R James D Dolphin T W Leung F W B Einstein
and A C Willis ldquoPreparation and characterization of someruthenium(III) porphyrins including the crystal structure ofbromo(octaethylporphinato)(triphenylphosphine)ruthenium(III)rdquoCanadian Journal of Chemistry vol 62 no 7 pp 1238ndash12451984
[57] M Plois R Wolf W Hujo and S Grimme ldquoTowards reagentsfor bimetallic activation reactions polyhydride complexes withRu2H3 Ru2ZnH6 and Cu
2Ru2H6coresrdquo European Journal of
Inorganic Chemistry vol 2013 no 17 pp 3039ndash3048 2013[58] L Hintermann L Xiao A Labonne and U Englert
ldquo[CpRu(1205786-naphthalene)]PF6as precursor in complex synthesis
and catalysis with the cyclopentadienyl-ruthenium(II) cationrdquoOrganometallics vol 28 no 19 pp 5739ndash5748 2009
[59] I W Wyman K N Robertson T S Cameron J C SwartsandM A S Aquino ldquoSynthesis structure and electrochemistryof (ferrocene-2-propenoato-OO1015840)bis[12-bis(diphenylphosphi-no)ethane-PP1015840]ruthenium(II) hexafluorophosphaterdquo Inorgan-ica Chimica Acta vol 359 no 9 pp 3092ndash3096 2006
[60] C A Vock C Scolaro A D Phillips R Scopelliti G Sava andP J Dyson ldquoSynthesis characterization and in vitro evaluationof novel ruthenium(II) 1205786-arene imidazole complexesrdquo Journalof Medicinal Chemistry vol 49 no 18 pp 5552ndash5561 2006
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
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Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 11
Table12Th
eassignm
ento
fthe
prom
inentIRvibrations
ofthem
odels
atdifferent
compu
tatio
nalm
etho
ds
B3LY
PCC
SDMP2
PBE
Ru-C
346783
9624120573(H
RuH)120592(Ru-H)
386628
124120573(H
RuH)120573(H
RuH)
120592(C
H)120592(Ru-H)
381759
1510
1120573(H
RuH)120573(H
RuH)
120591(H
RuHC)
30511
103120592(C
H)o(Ru
HCH
)120592(C
H)
313241
8772
120592(C
H)120592(C
H)
344585
6003
120592(Ru-H)
326534
582120573(H
CH)120592(C
H)120592(Ru-H)
3044
61
5191120592(C
H)o(Ru
HCH
)120592(Ru-H)
306501
5614120573(H
RuH)120573(H
RuH)
o(Ru
HCH
)323718
7402120573(H
CH)120573(H
RuH)120592(C
H)
310576
7913
120573(H
RuH)120592(Ru-H)
29104116677
120592(C
H)120592(C
H)
299873
14381
120592(C
H)120592(C
H)
310607
10481120573(H
RuC)
120591(H
CRuH
)o(Ru
HCH
)230969
6851120573(H
RuH)120591(H
RuHC)
120592(Ru-H)
247128
4498120573(H
RuH)o(Ru
HCH
)120592(Ru-H)
240085
1095
1120592(C
H)
231944
1014
7120573(H
RuC)
o(RuH
CH)
207553
969120573(H
RuH)120573(H
RuH)
120592(Ru-H)120592(Ru-H)
232314
1296
8120592(C
H)
Ru-N
38020714205120573(H
RuH)120573(H
RuH)
120573(H
RuH)
401043
1231120573(H
RuH)120591(H
RuHN)
120592(N
H)
403478
11428120591(H
RuNH)o(Ru
HNH)
120592(N
H)
353289
10673120573(H
RuH)120573(H
RuH)
339019
20019
120592(N
H)120592(N
H)
347897
18119120573(H
RuH)120573(H
RuH)
120591(H
RuHN)120592(Ru-H)
347497
1866120573(H
RuH)120573(H
RuH)
120592(Ru-H)
331504
19282
120592(N
H)120592(N
H)
32687139839
120592(N
H)120592(N
H)
336728
2897
5120592(Ru-H)
332695
1499
5120573(H
RuH)o(Ru
HNH)
318372
37524
120592(N
H)120592(N
H)
293151
4214120592(Ru-H)120592(Ru-H)120592(N
H)
120592(N
H)
327085
3514120573(H
RuH)120591(H
RuHN)
120592(Ru-H)
2746
17455
o(Ru
HNH)120592(Ru-H)
120592(Ru-H)
238961
4007120573(H
RuH)120592(Ru-H)
207916
6108
120592(Ru-H)
199979
4338
120573(H
NH)
210524
6443
o(Ru
HNH)120592(N
H)
120592(Ru-H)
203734
6557
120592(Ru-H)
Ru-O
372613
2694
9120592(O
H)
380749
28041
o(Ru
HOH)120592(Ru-H)
389061
1005
o(Ru
HOH)120573(H
RuH)
3608772399
3120592(O
H)
275932
1407120573(H
RuH)o(Ru
HOH)
o(Ru
HOH)120592(Ru-H)
31079
1921120573(H
RuO)120573(H
RuH)
o(Ru
HOH)
370979
51891120573(H
RuO)120573(H
RuO)
327956
2992120573(H
RuH)120573(H
RuH)
18598
2333
120592(Ru-H)120592(Ru-H)
179443
2374120573(H
RuH)o(Ru
HOH)
120592(Ru-H)
291506
5502
o(Ru
HOH)120592(Ru-H)
120592(Ru-H)
220079
1599120573(H
RuH)o(Ru
HOH)
120592(Ru-H)120592(Ru-H)
1346
08
2894120592(Ru-H)120592(Ru-H)
125632
2895120592(Ru-H)120573(H
ORu
)260461
4569120592(O
H)120573(H
ORu
)203014
1588
120592(Ru-H)
112741
9479120573(H
RuH)120592(Ru-H)
120592(Ru-H)
109235
7374
120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
205106
3383120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
147934
29120592(Ru-H)120592(Ru-H)
Ru-C
l185546
2458
120592(Ru-H)
308667
1411120573(H
RuH)o(Ru
HClH)
120592(Ru-H)
30365123653
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
22088
2242
120592(Ru-H)
131751
3288
120592(Ru-H)
179947
2511
o(Ru
HClH)120592(Ru-H)
120592(Ru-H)
261179
3015
120592(Ru-H)120573(H
RuH)
210816
1124
120592(Ru-H)
114581
9421
120592(Ru-H)
121159
3269120573(H
RuH)120573(H
RuH)
120573(H
RuCl)
20399
3006120573(H
RuH)120592(Ru-H)
120592(Ru-H)120573(H
RuH)
203112
1687
120592(Ru-H)
84759
3157
120592(Ru-H)
110861
7222
o(Ru
HClH)o(Ru
HClH)
120592(Ru-H)120573(H
RuCl)
131224
3565
o(Ru
HClH)120592(Ru-H)
120573(H
RuH)
147293
3151
120592(Ru-H)
79488
381
120573(H
RuH)
7687
2483120573(H
RuH)120592(Ru-H)
120592(Ru-H)120592(Ru-H)
109164
1501120592(Ru-H)120573(H
RuH)
11346
9195
3120573(H
RuH)
12 Journal of Chemistry
Table12C
ontin
ued
B3LY
PCC
SDMP2
PBE
Ru-P
384575
1547
120573(H
RuH)
40856716207120573(H
RuH)120591(H
RuPH
)o(Ru
HPH
)410148
11361120573(H
RuH)120573(H
RuH)
3509879645120573(H
RuH)120592(Ru-H)
296363
1457120573(H
RuH)120592(Ru-H)
328227
1508120573(H
RuH)120573(H
RuH)
120591(H
PRuH
)264975
4273
120573(H
RuP)120592(Ru-H)
246259
4871
120592(PH)120592(PH)
253628
4006
120592(PH)120592(PH)
261721
3138
120592(Ru-H)
262336
4752
120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
24307
5689
120592(PH)120592(PH)
250603
4624
120592(PH)120592(PH)
259379
3579
120573(H
RuP)
256933
4865120573(H
RuP)120573
(HRu
H)
238468
1306120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
245899
7096
120592(PH)120592(PH)
255419
4427120573(H
RuH)120591(H
PRuH
)120591(H
PRuH
)228633
8692
120573(H
RuH)120592(PH)
237354
92120592(PH)
Ru-S
265041
1308
120592(SH)
290793
378120573(H
RuH)120591(H
SRuH
)120592(Ru-H)120573(H
RuS)
417199
15487
o(Ru
HSH
)o(Ru
HSH
)120573(H
RuH)
34606
2384120573(H
RuH)120573(H
RuH)
120573(H
RuH)o(Ru
HSH
)
26342
1916
120573(H
RuH)120592(Ru-H)
188073
1685120573(H
RuH)120573(H
RuH)
120592(Ru-H)
28041
199265120573(H
RuS)120573
(HRu
H)
120573(H
RuH)120592(Ru-H)
258225
1254
120592(SH)
1913
1699
120592(Ru-H)
114853
2967120591(H
SRuH
)120592(SH)
120592(Ru-H)
2385442392374
120573(H
RuS)
21675
2604
120592(Ru-H)
121642
3386120592(Ru-H)120592(Ru-H)
109859
10132120573(H
RuH)120591(H
SRuH
)o(Ru
HSH
)120592(Ru-H)
225761
44894
120592(Ru-H)120573(H
RuH)
132047
3699120592(Ru-H)120592(Ru-H)
11086
11006120573(H
RuH)120592(Ru-H)
82534
331120591(H
SRuH
)120592(Ru-H)
120592(Ru-H)
210643
5205
120592(Ru-H)
8835
5098
o(Ru
HSH
)o(Ru
HSH
)120592(Ru-H)120592(Ru-H)
Journal of Chemistry 13
all the methods Ru-C Ru-N and Ru-O vibrations are withinthe range of 500 to 720 which is far higher than the rangeof vibrations of Ru-Cl Ru-P and Ru-S which are foundwithin the range of 224 to 658 Generally the order of Ru-L vibrations can be assumed as Ru-N gt Ru-O gt Ru-C gtRu-Cl gt Ru-S gt Ru-P (Table 11) The wavenumbers of thevibrations computed from the different methods appear to besignificantly different from each other in values and positions(Figure 3) The features of the IR spectra using MP2 andCCSD are very similar in the models Some vibration around291506 in model Ru-O 303651 in Ru-Cl and 238544 inRu-S are very prominent in MP2 methods compared to inany other methods or even absent in other methods Forinstance the bending of the angle of HRuS which is found tobe prominent in MP2 method is completely absent in othermethods (see Figure 3 and Table 12) The MP2 and CCSDshow strong vibrations within the range of 3800 to 4100 inmany of the models which are obviously absent in manyof the PBE and B3LYP methods Using the PED methodas implemented in VEDA package most of these vibrationsat high frequencies are a result of the torsional and out-of-plane vibration of H-Ru-X-H where X represents the typeof the model as shown in Table 12 In addition most of thebending vibrations which are determined by PBE and B3LYPfrom 2800 to 3800 in the models are also determined byMP2 and CCSD though some cases are at lower wavenumbercompared to PBE and B3LYP (Table 12) In the models Ru-Oand Ru-Cl PBE and B3LYP give priority to the OH and RuHvibrations respectively whileMP2 andCCSD give priority tothe torsional stretching and angle bending of their atoms
4 Conclusions
Six models of Ru-L bonds Ru-C Ru-N Ru-O Ru-Cl Ru-P and Ru-S are built to represent common rutheniumcomplexes and possible ruthenium-receptor interactionsThe reproducibility of their geometrical electronic spec-troscopic and conductive properties was investigated usingMP2 CCSD PBE and B3LYP functionals with differentcombination of basis sets Generally we observed that thereproducibility of most of the properties is much easier usingdifferent basis sets compared to using different functionalmethods as a result of significant geometrical changes whichis possible especially if there are many light atoms likehydrogen atoms as in themodelsThe order of the energy andthe thermodynamic properties are found to be reproducibleusing different functionalmethods and basis sets butHOMOLUMO 119869-coupling hyperpolarizabilities and isotropic andanisotropic shielding are found to depend more on the typeof the functional used rather than on the type of the basis setThe only significant similarity observed among the methodsapplied in computing hyperpolarizabilities is that they allrated models Ru-S Ru-Cl and Ru-O among their best threeThe optimized geometries and the thermodynamic proper-ties obtained from the functional PBE are found to be verysimilar to MP2 and perform better than B3LYP and CCSDwhich further give insight into many literaturesrsquo preferencefor PBE in optimizing metal complexes In computation ofthe isotropic and anisotropic shielding tensors B3LYP gives
values similar to MP2 and performs better than PBE The IRvibrations and assignment clearly show that the vibrationsobtained from the MP2 and CCSD methods are very similarand give preference to the torsional and bending vibrationsof the molecules over their stretching The order of the IRvibrations of the ruthenium-ligand bonds can be assumed asRu-N gt Ru-O gt Ru-C gt Ru-Cl gt Ru-S gt Ru-P
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
The authors gracefully acknowledged the financial support ofGovan Mbeki Research and Development Centre Universityof Fort Hare South Africa The CHPC in Republic ofSouth Africa is gracefully acknowledged for providing thecomputing facilities and some of the software used for thecomputation
References
[1] B Dutta R Scopelliti and K Severin ldquoSynthesis structure andreactivity of the methoxy-bridged dimer [CpandRu(120583-OMe)]
2
(Cpand = 1205785-1-methoxy-24-di-tert-butyl-3-neopentylcyclopenta-dienyl)rdquo Organometallics vol 27 no 3 pp 423ndash429 2008
[2] M A Furrer F Schmitt M Wiederkehr L Juillerat-Jeanneretand B Therrien ldquoCellular delivery of pyrenyl-arene rutheniumcomplexes by a water-soluble arene ruthenium metalla-cagerdquoDalton Transactions vol 41 no 24 pp 7201ndash7211 2012
[3] Q ZhouW Lei YChen et al ldquoRuthenium(II)-arene complexeswith strong fluorescence insight into the underlying mecha-nismrdquoChemistrymdashA European Journal vol 18 no 28 pp 8617ndash8621 2012
[4] L Bıro E Farkas and P Buglyo ldquoHydrolytic behaviour andchloride ion binding capability of [Ru(1205786 minus119901minus cym)(H
2O)3]2+
a solution equilibrium studyrdquoDalton Transactions vol 41 no 1pp 285ndash291 2012
[5] Y Boutadla D L Davies R C Jones and K Singh ldquoThescope of ambiphilic acetate-assisted cyclometallation with half-sandwich complexes of iridium rhodium and rutheniumrdquoChemistrymdashA European Journal vol 17 no 12 pp 3438ndash34482011
[6] Y F Han H Li Y Fei Y J Lin W Z Zhang and GX Jin ldquoSynthesis and structural characterization of binuclearhalf-sandwich iridium rhodium and ruthenium complexescontaining 441015840-dipyridyldisulfide (4DPDS) ligandsrdquo DaltonTransactions vol 39 no 30 pp 7119ndash7124 2010
[7] B Dutta B F Curchod P Campomanes et al ldquoReactions ofalkynes with [RuCl(cyclopentadienyl)] complexes the impor-tant first stepsrdquo ChemistrymdashA European Journal vol 16 no 28pp 8400ndash8409 2010
[8] M Jimenez-Tenorio M C Puerta P Valerga S MonchoG Ujaque and A Lledos ldquoProton-transfer reactions to half-sandwich ruthenium trihydride complexes bearing hemilabilePN ligands experimental and density functional theory stud-iesrdquo Inorganic Chemistry vol 49 no 13 pp 6035ndash6057 2010
14 Journal of Chemistry
[9] B Dutta C Scolaro R Scopelliti P J Dyson and K Sev-erin ldquoImportance of the 120587-ligand remarkable effect of thecyclopentadienyl ring on the cytotoxicity of ruthenium PTAcompoundsrdquoOrganometallics vol 27 no 7 pp 1355ndash1357 2008
[10] T Bugarcic A Habtemariam J Stepankova et al ldquoThe con-trasting chemistry and cancer cell cytotoxicity of bipyridineand bipyridinediol ruthenium(II) arene complexesrdquo InorganicChemistry vol 47 no 24 pp 11470ndash11486 2008
[11] M Castellano-Castillo H Kostrhunova V Marini et al ldquoBind-ing ofmismatch repair proteinMutS tomispairedDNA adductsof intercalating ruthenium(II) arene complexesrdquo Journal ofBiological Inorganic Chemistry vol 13 no 6 pp 993ndash999 2008
[12] S J Dougan A Habtemariam S E McHale S Parsons andP J Sadler ldquoCatalytic organometallic anticancer complexesrdquoProceedings of the National Academy of Sciences of the UnitedStates of America vol 105 no 33 pp 11628ndash11633 2008
[13] S J Dougan M Melchart A Habtemariam S Parsons and PJ Sadler ldquoPhenylazo-pyridine and phenylazo-pyrazole chloridoruthenium(II) arene complexes arene loss aquation and can-cer cell cytotoxicityrdquo Inorganic Chemistry vol 45 no 26 pp10882ndash10894 2006
[14] V Ritleng P Bertani M Pfeffer C Sirlin and J HirschingerldquoOptically active ortho-metalated half-sandwich rutheniumcomplexes solid-state NMR as a convenient tool to analyzemixtures of diastereomersrdquo Inorganic Chemistry vol 40 no 20pp 5117ndash5122 2001
[15] Y Sunada Y Hayashi H Kawaguchi and K TatsumildquoAlkynethiolato and alkyneselenolato rutheniumhalf-sandwichcomplexes Synthesis structures and reactions with (1205785ndashC5H5)2Zrrdquo Inorganic Chemistry vol 40 no 27 pp 7072ndash70782001
[16] K Yamanari R Ito S Yamamoto et al ldquoCyclic tetramerscomposed of rhodium(III) iridium(III) or ruthenium(II) half-sandwich and6-purinethionesrdquo Inorganic Chemistry vol 41 no25 pp 6824ndash6830 2002
[17] F Caruso M Rossi A Benson et al ldquoRuthenium-arenecomplexes of curcumin X-ray and density functional the-ory structure synthesis and spectroscopic characterizationin vitro antitumor activity and DNA docking studies of (p-cymene)Ru(curcuminato)chlorordquo Journal of Medicinal Chem-istry vol 55 no 3 pp 1072ndash1081 2012
[18] C Gossens I Tavernelli and U Rothlisberger ldquoBinding oforganometallic ruthenium(II) anticancer compounds to nucle-obases a computational studyrdquo Journal of Physical Chemistry Avol 113 no 43 pp 11888ndash11897 2009
[19] A M Pizarro A Habtemariam and P J Sadler ldquoActiva-tion mechanisms for organometallic anticancer complexesrdquoin Medicinal Organometallic Chemistry vol 32 of Topics inOrganometallic Chemistry pp 21ndash56 Springer Berlin Ger-many 2010
[20] I Turel and J Kljun ldquoInteractions of metal ions with DNAits constituents and derivatives which may be relevant foranticancer researchrdquoCurrent Topics inMedicinal Chemistry vol11 no 21 pp 2661ndash2687 2011
[21] G Gasser I Ott and N Metzler-Nolte ldquoOrganometallic anti-cancer compoundsrdquo Journal of Medicinal Chemistry vol 54 no1 pp 3ndash25 2011
[22] K J Kilpin S Crot T Riedel J A Kitchen and P JDyson ldquoRuthenium(II) and osmium(II) 123-triazolylideneorganometallics a preliminary investigation into the biologicalactivity of rsquoclickrsquo carbene complexesrdquo Dalton Transactions vol43 no 3 pp 1443ndash1448 2014
[23] A F A Peacock S Parsons and P J Sadler ldquoTuning thehydrolytic aqueous chemistry of osmium arene complexeswith NO-chelating ligands to achieve cancer cell cytotoxicityrdquoJournal of the American Chemical Society vol 129 no 11 pp3348ndash3357 2007
[24] A F A Peacock M Melchart R J Deeth A Habtemariam SParsons and P J Sadler ldquoOsmium(II) and ruthenium(II) arenemaltolato complexes rapid hydrolysis and nucleobase bindingrdquoChemistrymdashA European Journal vol 13 no 9 pp 2601ndash26132007
[25] F Pelletier V Comte A Massard et al ldquoDevelopment ofbimetallic titanoceneminusrutheniumminusarene complexes as anti-cancer agents relationships between structural and biologicalpropertiesrdquo Journal of Medicinal Chemistry vol 53 no 19 pp6923ndash6933 2010
[26] K J Kilpin and P J Dyson ldquoEnzyme inhibition by metalcomplexes concepts strategies and applicationsrdquo ChemicalScience vol 4 no 4 pp 1410ndash1419 2013
[27] G Gasser andNMetzler-Nolte ldquoThe potential of organometal-lic complexes in medicinal chemistryrdquo Current Opinion inChemical Biology vol 16 no 1-2 pp 84ndash91 2012
[28] I Turel J Kljun F Perdih et al ldquoFirst ruthenium organometal-lic complex of antibacterial agent ofloxacin Crystal structureand interactions with DNArdquo Inorganic Chemistry vol 49 no23 pp 10750ndash10752 2010
[29] C Adamo and V Barone ldquoToward reliable density functionalmethods without adjustable parameters the PBE0 modelrdquoJournal of Chemical Physics vol 110 no 13 pp 6158ndash6170 1999
[30] A D Becke ldquoDensity-functional thermochemistry IIIThe roleof exact exchangerdquoThe Journal of Chemical Physics vol 98 no7 article 5648 1993
[31] W J Stevens M Krauss H Basch and P G Jasien ldquoRelativisticcompact effective potentials and efficient shared-exponentbasis sets for the third- fourth- and fifth-row atomsrdquoCanadianJournal of Chemistry vol 70 no 2 pp 612ndash630 1992
[32] M J Frisch GW Trucks H B Schlegel et alOfficial Gaussian09 Literature Citation Gaussian Wallingford UK 2009
[33] D J Feller ldquoThe role of databases in support of computationalchemistry calculationsrdquo Journal of Computational Chemistryvol 17 no 13 pp 1571ndash1586 1996
[34] K L Schuchardt B T Didier T Elsethagen et al ldquoBasis setexchange a community database for computational sciencesrdquoJournal of Chemical Information andModeling vol 47 no 3 pp1045ndash1052 2007
[35] Y Liu C-G Liu S-L Sun G-C Yang and Y-Q QiuldquoRedox-switching second-order nonlinear optical responses ofNandNandN ruthenium complexesrdquo Computational and TheoreticalChemistry vol 979 pp 112ndash118 2012
[36] P S Liyanage R M de Silva and K M N de Silva ldquoNonlinearoptical (NLO) properties of novel organometallic complexeshigh accuracy density functional theory (DFT) calculationsrdquoJournal of Molecular Structure THEOCHEM vol 639 pp 195ndash201 2003
[37] MH Jamroz ldquoVibrational EnergyDistributionAnalysis VEDA4 ProgramrdquoWarsaw Poland 2004ndash2010 httpwwwsmmgpl
[38] M H Jamroz J C Dobrowolski and R Brzozowski ldquoVibra-tional modes of 26- 27- and 23-diisopropylnaphthalene ADFT studyrdquo Journal of Molecular Structure vol 787 no 1ndash3 pp172ndash183 2006
[39] M H Jamroz ldquoVibrational Energy Distribution Analysis(VEDA) scopes and limitationsrdquo Spectrochimica Acta AMolec-ular and Biomolecular Spectroscopy vol 114 pp 220ndash230 2013
Journal of Chemistry 15
[40] R Marchal P Carbonniere D Begue and C Pouchan ldquoStruc-tural and vibrational determination of small galliumndasharsenideclusters fromCCSD(T) andDFT calculationsrdquoChemical PhysicsLetters vol 453 no 1ndash3 pp 49ndash54 2008
[41] R Marchal P Carbonniere and C Pouchan ldquoStructural andvibrational properties prediction of Sn
119899Te119899clusters (n = 2ndash
8) using the GSAM approachrdquo Computational and TheoreticalChemistry vol 990 pp 100ndash105 2012
[42] T Helgaker M Jaszunski and M Pecul ldquoThe quantum-chemical calculation of NMR indirect spin-spin coupling con-stantsrdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 53 no 4 pp 249ndash268 2008
[43] F A Perras andD L Bryce ldquoTheoretical study of homonuclear Jcoupling between quadrupolar spins single-crystal DOR andJ-resolved NMRrdquo Journal of Magnetic Resonance vol 242 pp23ndash32 2014
[44] I D Burns A F Hill A J P White D J Williams and J DE T Wilton-Ely ldquoPolyazolyl chelate chemistry 61 bidentatecoordination of HB(pz)
3(pz = Pyrazol-1-yl) to ruthenium and
osmium crystal structure of [RuH(CO)(PPh3)2k2-HB(pz)
3]rdquo
Organometallics vol 17 no 8 pp 1552ndash1557 1998[45] M Al-Noaimi and M A AlDamen ldquoRuthenium complexes
incorporating azoimine and 120572-diamine based ligands synthe-sis crystal structure electrochemistry and DFT calculationrdquoInorganica Chimica Acta vol 387 pp 45ndash51 2012
[46] K Nakajima Y Ando H Mano and M Kojima ldquoPhotosub-stitution reactivity crystal structures and electrochemistry ofruthenium(II) (III) complexes containing tetradentate (O
2N2
S2N2 and P
2N2) Schiff base ligandsrdquo Inorganica Chimica Acta
vol 274 no 2 pp 184ndash191 1998[47] Z-L Lu K Eichele I Warad et al ldquoSupported organometal-
lic complexes XXXVIII [1] Bis(methoxyethyldimethlphos-phine)ruthenium(II) complexes as transfer hydrogenation cat-alystsrdquo Zeitschrift fur Anorganische und Allgemeine Chemie vol629 no 7-8 pp 1308ndash1315 2003
[48] R Gaur and L Mishra ldquoSynthesis and characterization ofRu(II)ndashDMSOndashClndashchalcone complexes DNA binding nucle-ase and topoisomerase II inhibitory activityrdquo Inorganic Chem-istry vol 51 no 5 pp 3059ndash3070 2012
[49] B Cebrian-Losantos E Reisner C R Kowol et al ldquoSynthesisand reactivity of the aquation product of the antitumor complextrans-[Ru IIICI
4(indazole)
2] minusrdquo Inorganic Chemistry vol 47 no
14 pp 6513ndash6523 2008[50] B T Rasley M Rapta and R J Kulawiec ldquoDiastereoselectivity
in enolate coordination in a new class of chiral rutheniumenolate complexesrdquo Organometallics vol 15 no 13 pp 2852ndash2854 1996
[51] S David R S Perkins F R Fronczek S Kasiri S S MandalandR S Srivastava ldquoSynthesis characterization and anticanceractivity of ruthenium-pyrazole complexesrdquo Journal of InorganicBiochemistry vol 111 pp 33ndash39 2012
[52] B Dutta E Solari S Gauthier R Scopelliti and K SeverinldquoRuthenium half-sandwich complexes with sterically demand-ing cyclopentadienyl ligandsrdquo Organometallics vol 26 no 19pp 4791ndash4799 2007
[53] G Turkoglu S Tampier F Strinitz F W Heinemann E Hub-ner and N Burzlaff ldquoRuthenium carbonyl complexes bearingbis(pyrazol-1-yl)carboxylato ligandsrdquo Organometallics vol 31no 6 pp 2166ndash2174 2012
[54] A K Renfrew A D Phillips E Tapavicza R ScopellitiU Rothlisberger and P J Dyson ldquoTuning the efficacy of
ruthenium(II)-arene (RAPTA) antitumor compounds with flu-orinated arene ligandsrdquo Organometallics vol 28 no 17 pp5061ndash5071 2009
[55] P M Jeffries R E Ellenwood and G S Girolami ldquoAnionicruthenium(II) alkyls with ancillary diene and dienyl ligandssynthesis and structures of [(12057821205782-C
7H8)RuMe
4]2minus and [(12057831205782-
C8H11)RuMe
3]2minusrdquo Inorganica Chimica Acta vol 361 no 1 pp
3165ndash3170 2008[56] B R James D Dolphin T W Leung F W B Einstein
and A C Willis ldquoPreparation and characterization of someruthenium(III) porphyrins including the crystal structure ofbromo(octaethylporphinato)(triphenylphosphine)ruthenium(III)rdquoCanadian Journal of Chemistry vol 62 no 7 pp 1238ndash12451984
[57] M Plois R Wolf W Hujo and S Grimme ldquoTowards reagentsfor bimetallic activation reactions polyhydride complexes withRu2H3 Ru2ZnH6 and Cu
2Ru2H6coresrdquo European Journal of
Inorganic Chemistry vol 2013 no 17 pp 3039ndash3048 2013[58] L Hintermann L Xiao A Labonne and U Englert
ldquo[CpRu(1205786-naphthalene)]PF6as precursor in complex synthesis
and catalysis with the cyclopentadienyl-ruthenium(II) cationrdquoOrganometallics vol 28 no 19 pp 5739ndash5748 2009
[59] I W Wyman K N Robertson T S Cameron J C SwartsandM A S Aquino ldquoSynthesis structure and electrochemistryof (ferrocene-2-propenoato-OO1015840)bis[12-bis(diphenylphosphi-no)ethane-PP1015840]ruthenium(II) hexafluorophosphaterdquo Inorgan-ica Chimica Acta vol 359 no 9 pp 3092ndash3096 2006
[60] C A Vock C Scolaro A D Phillips R Scopelliti G Sava andP J Dyson ldquoSynthesis characterization and in vitro evaluationof novel ruthenium(II) 1205786-arene imidazole complexesrdquo Journalof Medicinal Chemistry vol 49 no 18 pp 5552ndash5561 2006
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
12 Journal of Chemistry
Table12C
ontin
ued
B3LY
PCC
SDMP2
PBE
Ru-P
384575
1547
120573(H
RuH)
40856716207120573(H
RuH)120591(H
RuPH
)o(Ru
HPH
)410148
11361120573(H
RuH)120573(H
RuH)
3509879645120573(H
RuH)120592(Ru-H)
296363
1457120573(H
RuH)120592(Ru-H)
328227
1508120573(H
RuH)120573(H
RuH)
120591(H
PRuH
)264975
4273
120573(H
RuP)120592(Ru-H)
246259
4871
120592(PH)120592(PH)
253628
4006
120592(PH)120592(PH)
261721
3138
120592(Ru-H)
262336
4752
120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
24307
5689
120592(PH)120592(PH)
250603
4624
120592(PH)120592(PH)
259379
3579
120573(H
RuP)
256933
4865120573(H
RuP)120573
(HRu
H)
238468
1306120573(H
RuH)120591(H
RuPH
)120592(Ru-H)
245899
7096
120592(PH)120592(PH)
255419
4427120573(H
RuH)120591(H
PRuH
)120591(H
PRuH
)228633
8692
120573(H
RuH)120592(PH)
237354
92120592(PH)
Ru-S
265041
1308
120592(SH)
290793
378120573(H
RuH)120591(H
SRuH
)120592(Ru-H)120573(H
RuS)
417199
15487
o(Ru
HSH
)o(Ru
HSH
)120573(H
RuH)
34606
2384120573(H
RuH)120573(H
RuH)
120573(H
RuH)o(Ru
HSH
)
26342
1916
120573(H
RuH)120592(Ru-H)
188073
1685120573(H
RuH)120573(H
RuH)
120592(Ru-H)
28041
199265120573(H
RuS)120573
(HRu
H)
120573(H
RuH)120592(Ru-H)
258225
1254
120592(SH)
1913
1699
120592(Ru-H)
114853
2967120591(H
SRuH
)120592(SH)
120592(Ru-H)
2385442392374
120573(H
RuS)
21675
2604
120592(Ru-H)
121642
3386120592(Ru-H)120592(Ru-H)
109859
10132120573(H
RuH)120591(H
SRuH
)o(Ru
HSH
)120592(Ru-H)
225761
44894
120592(Ru-H)120573(H
RuH)
132047
3699120592(Ru-H)120592(Ru-H)
11086
11006120573(H
RuH)120592(Ru-H)
82534
331120591(H
SRuH
)120592(Ru-H)
120592(Ru-H)
210643
5205
120592(Ru-H)
8835
5098
o(Ru
HSH
)o(Ru
HSH
)120592(Ru-H)120592(Ru-H)
Journal of Chemistry 13
all the methods Ru-C Ru-N and Ru-O vibrations are withinthe range of 500 to 720 which is far higher than the rangeof vibrations of Ru-Cl Ru-P and Ru-S which are foundwithin the range of 224 to 658 Generally the order of Ru-L vibrations can be assumed as Ru-N gt Ru-O gt Ru-C gtRu-Cl gt Ru-S gt Ru-P (Table 11) The wavenumbers of thevibrations computed from the different methods appear to besignificantly different from each other in values and positions(Figure 3) The features of the IR spectra using MP2 andCCSD are very similar in the models Some vibration around291506 in model Ru-O 303651 in Ru-Cl and 238544 inRu-S are very prominent in MP2 methods compared to inany other methods or even absent in other methods Forinstance the bending of the angle of HRuS which is found tobe prominent in MP2 method is completely absent in othermethods (see Figure 3 and Table 12) The MP2 and CCSDshow strong vibrations within the range of 3800 to 4100 inmany of the models which are obviously absent in manyof the PBE and B3LYP methods Using the PED methodas implemented in VEDA package most of these vibrationsat high frequencies are a result of the torsional and out-of-plane vibration of H-Ru-X-H where X represents the typeof the model as shown in Table 12 In addition most of thebending vibrations which are determined by PBE and B3LYPfrom 2800 to 3800 in the models are also determined byMP2 and CCSD though some cases are at lower wavenumbercompared to PBE and B3LYP (Table 12) In the models Ru-Oand Ru-Cl PBE and B3LYP give priority to the OH and RuHvibrations respectively whileMP2 andCCSD give priority tothe torsional stretching and angle bending of their atoms
4 Conclusions
Six models of Ru-L bonds Ru-C Ru-N Ru-O Ru-Cl Ru-P and Ru-S are built to represent common rutheniumcomplexes and possible ruthenium-receptor interactionsThe reproducibility of their geometrical electronic spec-troscopic and conductive properties was investigated usingMP2 CCSD PBE and B3LYP functionals with differentcombination of basis sets Generally we observed that thereproducibility of most of the properties is much easier usingdifferent basis sets compared to using different functionalmethods as a result of significant geometrical changes whichis possible especially if there are many light atoms likehydrogen atoms as in themodelsThe order of the energy andthe thermodynamic properties are found to be reproducibleusing different functionalmethods and basis sets butHOMOLUMO 119869-coupling hyperpolarizabilities and isotropic andanisotropic shielding are found to depend more on the typeof the functional used rather than on the type of the basis setThe only significant similarity observed among the methodsapplied in computing hyperpolarizabilities is that they allrated models Ru-S Ru-Cl and Ru-O among their best threeThe optimized geometries and the thermodynamic proper-ties obtained from the functional PBE are found to be verysimilar to MP2 and perform better than B3LYP and CCSDwhich further give insight into many literaturesrsquo preferencefor PBE in optimizing metal complexes In computation ofthe isotropic and anisotropic shielding tensors B3LYP gives
values similar to MP2 and performs better than PBE The IRvibrations and assignment clearly show that the vibrationsobtained from the MP2 and CCSD methods are very similarand give preference to the torsional and bending vibrationsof the molecules over their stretching The order of the IRvibrations of the ruthenium-ligand bonds can be assumed asRu-N gt Ru-O gt Ru-C gt Ru-Cl gt Ru-S gt Ru-P
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
The authors gracefully acknowledged the financial support ofGovan Mbeki Research and Development Centre Universityof Fort Hare South Africa The CHPC in Republic ofSouth Africa is gracefully acknowledged for providing thecomputing facilities and some of the software used for thecomputation
References
[1] B Dutta R Scopelliti and K Severin ldquoSynthesis structure andreactivity of the methoxy-bridged dimer [CpandRu(120583-OMe)]
2
(Cpand = 1205785-1-methoxy-24-di-tert-butyl-3-neopentylcyclopenta-dienyl)rdquo Organometallics vol 27 no 3 pp 423ndash429 2008
[2] M A Furrer F Schmitt M Wiederkehr L Juillerat-Jeanneretand B Therrien ldquoCellular delivery of pyrenyl-arene rutheniumcomplexes by a water-soluble arene ruthenium metalla-cagerdquoDalton Transactions vol 41 no 24 pp 7201ndash7211 2012
[3] Q ZhouW Lei YChen et al ldquoRuthenium(II)-arene complexeswith strong fluorescence insight into the underlying mecha-nismrdquoChemistrymdashA European Journal vol 18 no 28 pp 8617ndash8621 2012
[4] L Bıro E Farkas and P Buglyo ldquoHydrolytic behaviour andchloride ion binding capability of [Ru(1205786 minus119901minus cym)(H
2O)3]2+
a solution equilibrium studyrdquoDalton Transactions vol 41 no 1pp 285ndash291 2012
[5] Y Boutadla D L Davies R C Jones and K Singh ldquoThescope of ambiphilic acetate-assisted cyclometallation with half-sandwich complexes of iridium rhodium and rutheniumrdquoChemistrymdashA European Journal vol 17 no 12 pp 3438ndash34482011
[6] Y F Han H Li Y Fei Y J Lin W Z Zhang and GX Jin ldquoSynthesis and structural characterization of binuclearhalf-sandwich iridium rhodium and ruthenium complexescontaining 441015840-dipyridyldisulfide (4DPDS) ligandsrdquo DaltonTransactions vol 39 no 30 pp 7119ndash7124 2010
[7] B Dutta B F Curchod P Campomanes et al ldquoReactions ofalkynes with [RuCl(cyclopentadienyl)] complexes the impor-tant first stepsrdquo ChemistrymdashA European Journal vol 16 no 28pp 8400ndash8409 2010
[8] M Jimenez-Tenorio M C Puerta P Valerga S MonchoG Ujaque and A Lledos ldquoProton-transfer reactions to half-sandwich ruthenium trihydride complexes bearing hemilabilePN ligands experimental and density functional theory stud-iesrdquo Inorganic Chemistry vol 49 no 13 pp 6035ndash6057 2010
14 Journal of Chemistry
[9] B Dutta C Scolaro R Scopelliti P J Dyson and K Sev-erin ldquoImportance of the 120587-ligand remarkable effect of thecyclopentadienyl ring on the cytotoxicity of ruthenium PTAcompoundsrdquoOrganometallics vol 27 no 7 pp 1355ndash1357 2008
[10] T Bugarcic A Habtemariam J Stepankova et al ldquoThe con-trasting chemistry and cancer cell cytotoxicity of bipyridineand bipyridinediol ruthenium(II) arene complexesrdquo InorganicChemistry vol 47 no 24 pp 11470ndash11486 2008
[11] M Castellano-Castillo H Kostrhunova V Marini et al ldquoBind-ing ofmismatch repair proteinMutS tomispairedDNA adductsof intercalating ruthenium(II) arene complexesrdquo Journal ofBiological Inorganic Chemistry vol 13 no 6 pp 993ndash999 2008
[12] S J Dougan A Habtemariam S E McHale S Parsons andP J Sadler ldquoCatalytic organometallic anticancer complexesrdquoProceedings of the National Academy of Sciences of the UnitedStates of America vol 105 no 33 pp 11628ndash11633 2008
[13] S J Dougan M Melchart A Habtemariam S Parsons and PJ Sadler ldquoPhenylazo-pyridine and phenylazo-pyrazole chloridoruthenium(II) arene complexes arene loss aquation and can-cer cell cytotoxicityrdquo Inorganic Chemistry vol 45 no 26 pp10882ndash10894 2006
[14] V Ritleng P Bertani M Pfeffer C Sirlin and J HirschingerldquoOptically active ortho-metalated half-sandwich rutheniumcomplexes solid-state NMR as a convenient tool to analyzemixtures of diastereomersrdquo Inorganic Chemistry vol 40 no 20pp 5117ndash5122 2001
[15] Y Sunada Y Hayashi H Kawaguchi and K TatsumildquoAlkynethiolato and alkyneselenolato rutheniumhalf-sandwichcomplexes Synthesis structures and reactions with (1205785ndashC5H5)2Zrrdquo Inorganic Chemistry vol 40 no 27 pp 7072ndash70782001
[16] K Yamanari R Ito S Yamamoto et al ldquoCyclic tetramerscomposed of rhodium(III) iridium(III) or ruthenium(II) half-sandwich and6-purinethionesrdquo Inorganic Chemistry vol 41 no25 pp 6824ndash6830 2002
[17] F Caruso M Rossi A Benson et al ldquoRuthenium-arenecomplexes of curcumin X-ray and density functional the-ory structure synthesis and spectroscopic characterizationin vitro antitumor activity and DNA docking studies of (p-cymene)Ru(curcuminato)chlorordquo Journal of Medicinal Chem-istry vol 55 no 3 pp 1072ndash1081 2012
[18] C Gossens I Tavernelli and U Rothlisberger ldquoBinding oforganometallic ruthenium(II) anticancer compounds to nucle-obases a computational studyrdquo Journal of Physical Chemistry Avol 113 no 43 pp 11888ndash11897 2009
[19] A M Pizarro A Habtemariam and P J Sadler ldquoActiva-tion mechanisms for organometallic anticancer complexesrdquoin Medicinal Organometallic Chemistry vol 32 of Topics inOrganometallic Chemistry pp 21ndash56 Springer Berlin Ger-many 2010
[20] I Turel and J Kljun ldquoInteractions of metal ions with DNAits constituents and derivatives which may be relevant foranticancer researchrdquoCurrent Topics inMedicinal Chemistry vol11 no 21 pp 2661ndash2687 2011
[21] G Gasser I Ott and N Metzler-Nolte ldquoOrganometallic anti-cancer compoundsrdquo Journal of Medicinal Chemistry vol 54 no1 pp 3ndash25 2011
[22] K J Kilpin S Crot T Riedel J A Kitchen and P JDyson ldquoRuthenium(II) and osmium(II) 123-triazolylideneorganometallics a preliminary investigation into the biologicalactivity of rsquoclickrsquo carbene complexesrdquo Dalton Transactions vol43 no 3 pp 1443ndash1448 2014
[23] A F A Peacock S Parsons and P J Sadler ldquoTuning thehydrolytic aqueous chemistry of osmium arene complexeswith NO-chelating ligands to achieve cancer cell cytotoxicityrdquoJournal of the American Chemical Society vol 129 no 11 pp3348ndash3357 2007
[24] A F A Peacock M Melchart R J Deeth A Habtemariam SParsons and P J Sadler ldquoOsmium(II) and ruthenium(II) arenemaltolato complexes rapid hydrolysis and nucleobase bindingrdquoChemistrymdashA European Journal vol 13 no 9 pp 2601ndash26132007
[25] F Pelletier V Comte A Massard et al ldquoDevelopment ofbimetallic titanoceneminusrutheniumminusarene complexes as anti-cancer agents relationships between structural and biologicalpropertiesrdquo Journal of Medicinal Chemistry vol 53 no 19 pp6923ndash6933 2010
[26] K J Kilpin and P J Dyson ldquoEnzyme inhibition by metalcomplexes concepts strategies and applicationsrdquo ChemicalScience vol 4 no 4 pp 1410ndash1419 2013
[27] G Gasser andNMetzler-Nolte ldquoThe potential of organometal-lic complexes in medicinal chemistryrdquo Current Opinion inChemical Biology vol 16 no 1-2 pp 84ndash91 2012
[28] I Turel J Kljun F Perdih et al ldquoFirst ruthenium organometal-lic complex of antibacterial agent ofloxacin Crystal structureand interactions with DNArdquo Inorganic Chemistry vol 49 no23 pp 10750ndash10752 2010
[29] C Adamo and V Barone ldquoToward reliable density functionalmethods without adjustable parameters the PBE0 modelrdquoJournal of Chemical Physics vol 110 no 13 pp 6158ndash6170 1999
[30] A D Becke ldquoDensity-functional thermochemistry IIIThe roleof exact exchangerdquoThe Journal of Chemical Physics vol 98 no7 article 5648 1993
[31] W J Stevens M Krauss H Basch and P G Jasien ldquoRelativisticcompact effective potentials and efficient shared-exponentbasis sets for the third- fourth- and fifth-row atomsrdquoCanadianJournal of Chemistry vol 70 no 2 pp 612ndash630 1992
[32] M J Frisch GW Trucks H B Schlegel et alOfficial Gaussian09 Literature Citation Gaussian Wallingford UK 2009
[33] D J Feller ldquoThe role of databases in support of computationalchemistry calculationsrdquo Journal of Computational Chemistryvol 17 no 13 pp 1571ndash1586 1996
[34] K L Schuchardt B T Didier T Elsethagen et al ldquoBasis setexchange a community database for computational sciencesrdquoJournal of Chemical Information andModeling vol 47 no 3 pp1045ndash1052 2007
[35] Y Liu C-G Liu S-L Sun G-C Yang and Y-Q QiuldquoRedox-switching second-order nonlinear optical responses ofNandNandN ruthenium complexesrdquo Computational and TheoreticalChemistry vol 979 pp 112ndash118 2012
[36] P S Liyanage R M de Silva and K M N de Silva ldquoNonlinearoptical (NLO) properties of novel organometallic complexeshigh accuracy density functional theory (DFT) calculationsrdquoJournal of Molecular Structure THEOCHEM vol 639 pp 195ndash201 2003
[37] MH Jamroz ldquoVibrational EnergyDistributionAnalysis VEDA4 ProgramrdquoWarsaw Poland 2004ndash2010 httpwwwsmmgpl
[38] M H Jamroz J C Dobrowolski and R Brzozowski ldquoVibra-tional modes of 26- 27- and 23-diisopropylnaphthalene ADFT studyrdquo Journal of Molecular Structure vol 787 no 1ndash3 pp172ndash183 2006
[39] M H Jamroz ldquoVibrational Energy Distribution Analysis(VEDA) scopes and limitationsrdquo Spectrochimica Acta AMolec-ular and Biomolecular Spectroscopy vol 114 pp 220ndash230 2013
Journal of Chemistry 15
[40] R Marchal P Carbonniere D Begue and C Pouchan ldquoStruc-tural and vibrational determination of small galliumndasharsenideclusters fromCCSD(T) andDFT calculationsrdquoChemical PhysicsLetters vol 453 no 1ndash3 pp 49ndash54 2008
[41] R Marchal P Carbonniere and C Pouchan ldquoStructural andvibrational properties prediction of Sn
119899Te119899clusters (n = 2ndash
8) using the GSAM approachrdquo Computational and TheoreticalChemistry vol 990 pp 100ndash105 2012
[42] T Helgaker M Jaszunski and M Pecul ldquoThe quantum-chemical calculation of NMR indirect spin-spin coupling con-stantsrdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 53 no 4 pp 249ndash268 2008
[43] F A Perras andD L Bryce ldquoTheoretical study of homonuclear Jcoupling between quadrupolar spins single-crystal DOR andJ-resolved NMRrdquo Journal of Magnetic Resonance vol 242 pp23ndash32 2014
[44] I D Burns A F Hill A J P White D J Williams and J DE T Wilton-Ely ldquoPolyazolyl chelate chemistry 61 bidentatecoordination of HB(pz)
3(pz = Pyrazol-1-yl) to ruthenium and
osmium crystal structure of [RuH(CO)(PPh3)2k2-HB(pz)
3]rdquo
Organometallics vol 17 no 8 pp 1552ndash1557 1998[45] M Al-Noaimi and M A AlDamen ldquoRuthenium complexes
incorporating azoimine and 120572-diamine based ligands synthe-sis crystal structure electrochemistry and DFT calculationrdquoInorganica Chimica Acta vol 387 pp 45ndash51 2012
[46] K Nakajima Y Ando H Mano and M Kojima ldquoPhotosub-stitution reactivity crystal structures and electrochemistry ofruthenium(II) (III) complexes containing tetradentate (O
2N2
S2N2 and P
2N2) Schiff base ligandsrdquo Inorganica Chimica Acta
vol 274 no 2 pp 184ndash191 1998[47] Z-L Lu K Eichele I Warad et al ldquoSupported organometal-
lic complexes XXXVIII [1] Bis(methoxyethyldimethlphos-phine)ruthenium(II) complexes as transfer hydrogenation cat-alystsrdquo Zeitschrift fur Anorganische und Allgemeine Chemie vol629 no 7-8 pp 1308ndash1315 2003
[48] R Gaur and L Mishra ldquoSynthesis and characterization ofRu(II)ndashDMSOndashClndashchalcone complexes DNA binding nucle-ase and topoisomerase II inhibitory activityrdquo Inorganic Chem-istry vol 51 no 5 pp 3059ndash3070 2012
[49] B Cebrian-Losantos E Reisner C R Kowol et al ldquoSynthesisand reactivity of the aquation product of the antitumor complextrans-[Ru IIICI
4(indazole)
2] minusrdquo Inorganic Chemistry vol 47 no
14 pp 6513ndash6523 2008[50] B T Rasley M Rapta and R J Kulawiec ldquoDiastereoselectivity
in enolate coordination in a new class of chiral rutheniumenolate complexesrdquo Organometallics vol 15 no 13 pp 2852ndash2854 1996
[51] S David R S Perkins F R Fronczek S Kasiri S S MandalandR S Srivastava ldquoSynthesis characterization and anticanceractivity of ruthenium-pyrazole complexesrdquo Journal of InorganicBiochemistry vol 111 pp 33ndash39 2012
[52] B Dutta E Solari S Gauthier R Scopelliti and K SeverinldquoRuthenium half-sandwich complexes with sterically demand-ing cyclopentadienyl ligandsrdquo Organometallics vol 26 no 19pp 4791ndash4799 2007
[53] G Turkoglu S Tampier F Strinitz F W Heinemann E Hub-ner and N Burzlaff ldquoRuthenium carbonyl complexes bearingbis(pyrazol-1-yl)carboxylato ligandsrdquo Organometallics vol 31no 6 pp 2166ndash2174 2012
[54] A K Renfrew A D Phillips E Tapavicza R ScopellitiU Rothlisberger and P J Dyson ldquoTuning the efficacy of
ruthenium(II)-arene (RAPTA) antitumor compounds with flu-orinated arene ligandsrdquo Organometallics vol 28 no 17 pp5061ndash5071 2009
[55] P M Jeffries R E Ellenwood and G S Girolami ldquoAnionicruthenium(II) alkyls with ancillary diene and dienyl ligandssynthesis and structures of [(12057821205782-C
7H8)RuMe
4]2minus and [(12057831205782-
C8H11)RuMe
3]2minusrdquo Inorganica Chimica Acta vol 361 no 1 pp
3165ndash3170 2008[56] B R James D Dolphin T W Leung F W B Einstein
and A C Willis ldquoPreparation and characterization of someruthenium(III) porphyrins including the crystal structure ofbromo(octaethylporphinato)(triphenylphosphine)ruthenium(III)rdquoCanadian Journal of Chemistry vol 62 no 7 pp 1238ndash12451984
[57] M Plois R Wolf W Hujo and S Grimme ldquoTowards reagentsfor bimetallic activation reactions polyhydride complexes withRu2H3 Ru2ZnH6 and Cu
2Ru2H6coresrdquo European Journal of
Inorganic Chemistry vol 2013 no 17 pp 3039ndash3048 2013[58] L Hintermann L Xiao A Labonne and U Englert
ldquo[CpRu(1205786-naphthalene)]PF6as precursor in complex synthesis
and catalysis with the cyclopentadienyl-ruthenium(II) cationrdquoOrganometallics vol 28 no 19 pp 5739ndash5748 2009
[59] I W Wyman K N Robertson T S Cameron J C SwartsandM A S Aquino ldquoSynthesis structure and electrochemistryof (ferrocene-2-propenoato-OO1015840)bis[12-bis(diphenylphosphi-no)ethane-PP1015840]ruthenium(II) hexafluorophosphaterdquo Inorgan-ica Chimica Acta vol 359 no 9 pp 3092ndash3096 2006
[60] C A Vock C Scolaro A D Phillips R Scopelliti G Sava andP J Dyson ldquoSynthesis characterization and in vitro evaluationof novel ruthenium(II) 1205786-arene imidazole complexesrdquo Journalof Medicinal Chemistry vol 49 no 18 pp 5552ndash5561 2006
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 13
all the methods Ru-C Ru-N and Ru-O vibrations are withinthe range of 500 to 720 which is far higher than the rangeof vibrations of Ru-Cl Ru-P and Ru-S which are foundwithin the range of 224 to 658 Generally the order of Ru-L vibrations can be assumed as Ru-N gt Ru-O gt Ru-C gtRu-Cl gt Ru-S gt Ru-P (Table 11) The wavenumbers of thevibrations computed from the different methods appear to besignificantly different from each other in values and positions(Figure 3) The features of the IR spectra using MP2 andCCSD are very similar in the models Some vibration around291506 in model Ru-O 303651 in Ru-Cl and 238544 inRu-S are very prominent in MP2 methods compared to inany other methods or even absent in other methods Forinstance the bending of the angle of HRuS which is found tobe prominent in MP2 method is completely absent in othermethods (see Figure 3 and Table 12) The MP2 and CCSDshow strong vibrations within the range of 3800 to 4100 inmany of the models which are obviously absent in manyof the PBE and B3LYP methods Using the PED methodas implemented in VEDA package most of these vibrationsat high frequencies are a result of the torsional and out-of-plane vibration of H-Ru-X-H where X represents the typeof the model as shown in Table 12 In addition most of thebending vibrations which are determined by PBE and B3LYPfrom 2800 to 3800 in the models are also determined byMP2 and CCSD though some cases are at lower wavenumbercompared to PBE and B3LYP (Table 12) In the models Ru-Oand Ru-Cl PBE and B3LYP give priority to the OH and RuHvibrations respectively whileMP2 andCCSD give priority tothe torsional stretching and angle bending of their atoms
4 Conclusions
Six models of Ru-L bonds Ru-C Ru-N Ru-O Ru-Cl Ru-P and Ru-S are built to represent common rutheniumcomplexes and possible ruthenium-receptor interactionsThe reproducibility of their geometrical electronic spec-troscopic and conductive properties was investigated usingMP2 CCSD PBE and B3LYP functionals with differentcombination of basis sets Generally we observed that thereproducibility of most of the properties is much easier usingdifferent basis sets compared to using different functionalmethods as a result of significant geometrical changes whichis possible especially if there are many light atoms likehydrogen atoms as in themodelsThe order of the energy andthe thermodynamic properties are found to be reproducibleusing different functionalmethods and basis sets butHOMOLUMO 119869-coupling hyperpolarizabilities and isotropic andanisotropic shielding are found to depend more on the typeof the functional used rather than on the type of the basis setThe only significant similarity observed among the methodsapplied in computing hyperpolarizabilities is that they allrated models Ru-S Ru-Cl and Ru-O among their best threeThe optimized geometries and the thermodynamic proper-ties obtained from the functional PBE are found to be verysimilar to MP2 and perform better than B3LYP and CCSDwhich further give insight into many literaturesrsquo preferencefor PBE in optimizing metal complexes In computation ofthe isotropic and anisotropic shielding tensors B3LYP gives
values similar to MP2 and performs better than PBE The IRvibrations and assignment clearly show that the vibrationsobtained from the MP2 and CCSD methods are very similarand give preference to the torsional and bending vibrationsof the molecules over their stretching The order of the IRvibrations of the ruthenium-ligand bonds can be assumed asRu-N gt Ru-O gt Ru-C gt Ru-Cl gt Ru-S gt Ru-P
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
The authors gracefully acknowledged the financial support ofGovan Mbeki Research and Development Centre Universityof Fort Hare South Africa The CHPC in Republic ofSouth Africa is gracefully acknowledged for providing thecomputing facilities and some of the software used for thecomputation
References
[1] B Dutta R Scopelliti and K Severin ldquoSynthesis structure andreactivity of the methoxy-bridged dimer [CpandRu(120583-OMe)]
2
(Cpand = 1205785-1-methoxy-24-di-tert-butyl-3-neopentylcyclopenta-dienyl)rdquo Organometallics vol 27 no 3 pp 423ndash429 2008
[2] M A Furrer F Schmitt M Wiederkehr L Juillerat-Jeanneretand B Therrien ldquoCellular delivery of pyrenyl-arene rutheniumcomplexes by a water-soluble arene ruthenium metalla-cagerdquoDalton Transactions vol 41 no 24 pp 7201ndash7211 2012
[3] Q ZhouW Lei YChen et al ldquoRuthenium(II)-arene complexeswith strong fluorescence insight into the underlying mecha-nismrdquoChemistrymdashA European Journal vol 18 no 28 pp 8617ndash8621 2012
[4] L Bıro E Farkas and P Buglyo ldquoHydrolytic behaviour andchloride ion binding capability of [Ru(1205786 minus119901minus cym)(H
2O)3]2+
a solution equilibrium studyrdquoDalton Transactions vol 41 no 1pp 285ndash291 2012
[5] Y Boutadla D L Davies R C Jones and K Singh ldquoThescope of ambiphilic acetate-assisted cyclometallation with half-sandwich complexes of iridium rhodium and rutheniumrdquoChemistrymdashA European Journal vol 17 no 12 pp 3438ndash34482011
[6] Y F Han H Li Y Fei Y J Lin W Z Zhang and GX Jin ldquoSynthesis and structural characterization of binuclearhalf-sandwich iridium rhodium and ruthenium complexescontaining 441015840-dipyridyldisulfide (4DPDS) ligandsrdquo DaltonTransactions vol 39 no 30 pp 7119ndash7124 2010
[7] B Dutta B F Curchod P Campomanes et al ldquoReactions ofalkynes with [RuCl(cyclopentadienyl)] complexes the impor-tant first stepsrdquo ChemistrymdashA European Journal vol 16 no 28pp 8400ndash8409 2010
[8] M Jimenez-Tenorio M C Puerta P Valerga S MonchoG Ujaque and A Lledos ldquoProton-transfer reactions to half-sandwich ruthenium trihydride complexes bearing hemilabilePN ligands experimental and density functional theory stud-iesrdquo Inorganic Chemistry vol 49 no 13 pp 6035ndash6057 2010
14 Journal of Chemistry
[9] B Dutta C Scolaro R Scopelliti P J Dyson and K Sev-erin ldquoImportance of the 120587-ligand remarkable effect of thecyclopentadienyl ring on the cytotoxicity of ruthenium PTAcompoundsrdquoOrganometallics vol 27 no 7 pp 1355ndash1357 2008
[10] T Bugarcic A Habtemariam J Stepankova et al ldquoThe con-trasting chemistry and cancer cell cytotoxicity of bipyridineand bipyridinediol ruthenium(II) arene complexesrdquo InorganicChemistry vol 47 no 24 pp 11470ndash11486 2008
[11] M Castellano-Castillo H Kostrhunova V Marini et al ldquoBind-ing ofmismatch repair proteinMutS tomispairedDNA adductsof intercalating ruthenium(II) arene complexesrdquo Journal ofBiological Inorganic Chemistry vol 13 no 6 pp 993ndash999 2008
[12] S J Dougan A Habtemariam S E McHale S Parsons andP J Sadler ldquoCatalytic organometallic anticancer complexesrdquoProceedings of the National Academy of Sciences of the UnitedStates of America vol 105 no 33 pp 11628ndash11633 2008
[13] S J Dougan M Melchart A Habtemariam S Parsons and PJ Sadler ldquoPhenylazo-pyridine and phenylazo-pyrazole chloridoruthenium(II) arene complexes arene loss aquation and can-cer cell cytotoxicityrdquo Inorganic Chemistry vol 45 no 26 pp10882ndash10894 2006
[14] V Ritleng P Bertani M Pfeffer C Sirlin and J HirschingerldquoOptically active ortho-metalated half-sandwich rutheniumcomplexes solid-state NMR as a convenient tool to analyzemixtures of diastereomersrdquo Inorganic Chemistry vol 40 no 20pp 5117ndash5122 2001
[15] Y Sunada Y Hayashi H Kawaguchi and K TatsumildquoAlkynethiolato and alkyneselenolato rutheniumhalf-sandwichcomplexes Synthesis structures and reactions with (1205785ndashC5H5)2Zrrdquo Inorganic Chemistry vol 40 no 27 pp 7072ndash70782001
[16] K Yamanari R Ito S Yamamoto et al ldquoCyclic tetramerscomposed of rhodium(III) iridium(III) or ruthenium(II) half-sandwich and6-purinethionesrdquo Inorganic Chemistry vol 41 no25 pp 6824ndash6830 2002
[17] F Caruso M Rossi A Benson et al ldquoRuthenium-arenecomplexes of curcumin X-ray and density functional the-ory structure synthesis and spectroscopic characterizationin vitro antitumor activity and DNA docking studies of (p-cymene)Ru(curcuminato)chlorordquo Journal of Medicinal Chem-istry vol 55 no 3 pp 1072ndash1081 2012
[18] C Gossens I Tavernelli and U Rothlisberger ldquoBinding oforganometallic ruthenium(II) anticancer compounds to nucle-obases a computational studyrdquo Journal of Physical Chemistry Avol 113 no 43 pp 11888ndash11897 2009
[19] A M Pizarro A Habtemariam and P J Sadler ldquoActiva-tion mechanisms for organometallic anticancer complexesrdquoin Medicinal Organometallic Chemistry vol 32 of Topics inOrganometallic Chemistry pp 21ndash56 Springer Berlin Ger-many 2010
[20] I Turel and J Kljun ldquoInteractions of metal ions with DNAits constituents and derivatives which may be relevant foranticancer researchrdquoCurrent Topics inMedicinal Chemistry vol11 no 21 pp 2661ndash2687 2011
[21] G Gasser I Ott and N Metzler-Nolte ldquoOrganometallic anti-cancer compoundsrdquo Journal of Medicinal Chemistry vol 54 no1 pp 3ndash25 2011
[22] K J Kilpin S Crot T Riedel J A Kitchen and P JDyson ldquoRuthenium(II) and osmium(II) 123-triazolylideneorganometallics a preliminary investigation into the biologicalactivity of rsquoclickrsquo carbene complexesrdquo Dalton Transactions vol43 no 3 pp 1443ndash1448 2014
[23] A F A Peacock S Parsons and P J Sadler ldquoTuning thehydrolytic aqueous chemistry of osmium arene complexeswith NO-chelating ligands to achieve cancer cell cytotoxicityrdquoJournal of the American Chemical Society vol 129 no 11 pp3348ndash3357 2007
[24] A F A Peacock M Melchart R J Deeth A Habtemariam SParsons and P J Sadler ldquoOsmium(II) and ruthenium(II) arenemaltolato complexes rapid hydrolysis and nucleobase bindingrdquoChemistrymdashA European Journal vol 13 no 9 pp 2601ndash26132007
[25] F Pelletier V Comte A Massard et al ldquoDevelopment ofbimetallic titanoceneminusrutheniumminusarene complexes as anti-cancer agents relationships between structural and biologicalpropertiesrdquo Journal of Medicinal Chemistry vol 53 no 19 pp6923ndash6933 2010
[26] K J Kilpin and P J Dyson ldquoEnzyme inhibition by metalcomplexes concepts strategies and applicationsrdquo ChemicalScience vol 4 no 4 pp 1410ndash1419 2013
[27] G Gasser andNMetzler-Nolte ldquoThe potential of organometal-lic complexes in medicinal chemistryrdquo Current Opinion inChemical Biology vol 16 no 1-2 pp 84ndash91 2012
[28] I Turel J Kljun F Perdih et al ldquoFirst ruthenium organometal-lic complex of antibacterial agent ofloxacin Crystal structureand interactions with DNArdquo Inorganic Chemistry vol 49 no23 pp 10750ndash10752 2010
[29] C Adamo and V Barone ldquoToward reliable density functionalmethods without adjustable parameters the PBE0 modelrdquoJournal of Chemical Physics vol 110 no 13 pp 6158ndash6170 1999
[30] A D Becke ldquoDensity-functional thermochemistry IIIThe roleof exact exchangerdquoThe Journal of Chemical Physics vol 98 no7 article 5648 1993
[31] W J Stevens M Krauss H Basch and P G Jasien ldquoRelativisticcompact effective potentials and efficient shared-exponentbasis sets for the third- fourth- and fifth-row atomsrdquoCanadianJournal of Chemistry vol 70 no 2 pp 612ndash630 1992
[32] M J Frisch GW Trucks H B Schlegel et alOfficial Gaussian09 Literature Citation Gaussian Wallingford UK 2009
[33] D J Feller ldquoThe role of databases in support of computationalchemistry calculationsrdquo Journal of Computational Chemistryvol 17 no 13 pp 1571ndash1586 1996
[34] K L Schuchardt B T Didier T Elsethagen et al ldquoBasis setexchange a community database for computational sciencesrdquoJournal of Chemical Information andModeling vol 47 no 3 pp1045ndash1052 2007
[35] Y Liu C-G Liu S-L Sun G-C Yang and Y-Q QiuldquoRedox-switching second-order nonlinear optical responses ofNandNandN ruthenium complexesrdquo Computational and TheoreticalChemistry vol 979 pp 112ndash118 2012
[36] P S Liyanage R M de Silva and K M N de Silva ldquoNonlinearoptical (NLO) properties of novel organometallic complexeshigh accuracy density functional theory (DFT) calculationsrdquoJournal of Molecular Structure THEOCHEM vol 639 pp 195ndash201 2003
[37] MH Jamroz ldquoVibrational EnergyDistributionAnalysis VEDA4 ProgramrdquoWarsaw Poland 2004ndash2010 httpwwwsmmgpl
[38] M H Jamroz J C Dobrowolski and R Brzozowski ldquoVibra-tional modes of 26- 27- and 23-diisopropylnaphthalene ADFT studyrdquo Journal of Molecular Structure vol 787 no 1ndash3 pp172ndash183 2006
[39] M H Jamroz ldquoVibrational Energy Distribution Analysis(VEDA) scopes and limitationsrdquo Spectrochimica Acta AMolec-ular and Biomolecular Spectroscopy vol 114 pp 220ndash230 2013
Journal of Chemistry 15
[40] R Marchal P Carbonniere D Begue and C Pouchan ldquoStruc-tural and vibrational determination of small galliumndasharsenideclusters fromCCSD(T) andDFT calculationsrdquoChemical PhysicsLetters vol 453 no 1ndash3 pp 49ndash54 2008
[41] R Marchal P Carbonniere and C Pouchan ldquoStructural andvibrational properties prediction of Sn
119899Te119899clusters (n = 2ndash
8) using the GSAM approachrdquo Computational and TheoreticalChemistry vol 990 pp 100ndash105 2012
[42] T Helgaker M Jaszunski and M Pecul ldquoThe quantum-chemical calculation of NMR indirect spin-spin coupling con-stantsrdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 53 no 4 pp 249ndash268 2008
[43] F A Perras andD L Bryce ldquoTheoretical study of homonuclear Jcoupling between quadrupolar spins single-crystal DOR andJ-resolved NMRrdquo Journal of Magnetic Resonance vol 242 pp23ndash32 2014
[44] I D Burns A F Hill A J P White D J Williams and J DE T Wilton-Ely ldquoPolyazolyl chelate chemistry 61 bidentatecoordination of HB(pz)
3(pz = Pyrazol-1-yl) to ruthenium and
osmium crystal structure of [RuH(CO)(PPh3)2k2-HB(pz)
3]rdquo
Organometallics vol 17 no 8 pp 1552ndash1557 1998[45] M Al-Noaimi and M A AlDamen ldquoRuthenium complexes
incorporating azoimine and 120572-diamine based ligands synthe-sis crystal structure electrochemistry and DFT calculationrdquoInorganica Chimica Acta vol 387 pp 45ndash51 2012
[46] K Nakajima Y Ando H Mano and M Kojima ldquoPhotosub-stitution reactivity crystal structures and electrochemistry ofruthenium(II) (III) complexes containing tetradentate (O
2N2
S2N2 and P
2N2) Schiff base ligandsrdquo Inorganica Chimica Acta
vol 274 no 2 pp 184ndash191 1998[47] Z-L Lu K Eichele I Warad et al ldquoSupported organometal-
lic complexes XXXVIII [1] Bis(methoxyethyldimethlphos-phine)ruthenium(II) complexes as transfer hydrogenation cat-alystsrdquo Zeitschrift fur Anorganische und Allgemeine Chemie vol629 no 7-8 pp 1308ndash1315 2003
[48] R Gaur and L Mishra ldquoSynthesis and characterization ofRu(II)ndashDMSOndashClndashchalcone complexes DNA binding nucle-ase and topoisomerase II inhibitory activityrdquo Inorganic Chem-istry vol 51 no 5 pp 3059ndash3070 2012
[49] B Cebrian-Losantos E Reisner C R Kowol et al ldquoSynthesisand reactivity of the aquation product of the antitumor complextrans-[Ru IIICI
4(indazole)
2] minusrdquo Inorganic Chemistry vol 47 no
14 pp 6513ndash6523 2008[50] B T Rasley M Rapta and R J Kulawiec ldquoDiastereoselectivity
in enolate coordination in a new class of chiral rutheniumenolate complexesrdquo Organometallics vol 15 no 13 pp 2852ndash2854 1996
[51] S David R S Perkins F R Fronczek S Kasiri S S MandalandR S Srivastava ldquoSynthesis characterization and anticanceractivity of ruthenium-pyrazole complexesrdquo Journal of InorganicBiochemistry vol 111 pp 33ndash39 2012
[52] B Dutta E Solari S Gauthier R Scopelliti and K SeverinldquoRuthenium half-sandwich complexes with sterically demand-ing cyclopentadienyl ligandsrdquo Organometallics vol 26 no 19pp 4791ndash4799 2007
[53] G Turkoglu S Tampier F Strinitz F W Heinemann E Hub-ner and N Burzlaff ldquoRuthenium carbonyl complexes bearingbis(pyrazol-1-yl)carboxylato ligandsrdquo Organometallics vol 31no 6 pp 2166ndash2174 2012
[54] A K Renfrew A D Phillips E Tapavicza R ScopellitiU Rothlisberger and P J Dyson ldquoTuning the efficacy of
ruthenium(II)-arene (RAPTA) antitumor compounds with flu-orinated arene ligandsrdquo Organometallics vol 28 no 17 pp5061ndash5071 2009
[55] P M Jeffries R E Ellenwood and G S Girolami ldquoAnionicruthenium(II) alkyls with ancillary diene and dienyl ligandssynthesis and structures of [(12057821205782-C
7H8)RuMe
4]2minus and [(12057831205782-
C8H11)RuMe
3]2minusrdquo Inorganica Chimica Acta vol 361 no 1 pp
3165ndash3170 2008[56] B R James D Dolphin T W Leung F W B Einstein
and A C Willis ldquoPreparation and characterization of someruthenium(III) porphyrins including the crystal structure ofbromo(octaethylporphinato)(triphenylphosphine)ruthenium(III)rdquoCanadian Journal of Chemistry vol 62 no 7 pp 1238ndash12451984
[57] M Plois R Wolf W Hujo and S Grimme ldquoTowards reagentsfor bimetallic activation reactions polyhydride complexes withRu2H3 Ru2ZnH6 and Cu
2Ru2H6coresrdquo European Journal of
Inorganic Chemistry vol 2013 no 17 pp 3039ndash3048 2013[58] L Hintermann L Xiao A Labonne and U Englert
ldquo[CpRu(1205786-naphthalene)]PF6as precursor in complex synthesis
and catalysis with the cyclopentadienyl-ruthenium(II) cationrdquoOrganometallics vol 28 no 19 pp 5739ndash5748 2009
[59] I W Wyman K N Robertson T S Cameron J C SwartsandM A S Aquino ldquoSynthesis structure and electrochemistryof (ferrocene-2-propenoato-OO1015840)bis[12-bis(diphenylphosphi-no)ethane-PP1015840]ruthenium(II) hexafluorophosphaterdquo Inorgan-ica Chimica Acta vol 359 no 9 pp 3092ndash3096 2006
[60] C A Vock C Scolaro A D Phillips R Scopelliti G Sava andP J Dyson ldquoSynthesis characterization and in vitro evaluationof novel ruthenium(II) 1205786-arene imidazole complexesrdquo Journalof Medicinal Chemistry vol 49 no 18 pp 5552ndash5561 2006
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
14 Journal of Chemistry
[9] B Dutta C Scolaro R Scopelliti P J Dyson and K Sev-erin ldquoImportance of the 120587-ligand remarkable effect of thecyclopentadienyl ring on the cytotoxicity of ruthenium PTAcompoundsrdquoOrganometallics vol 27 no 7 pp 1355ndash1357 2008
[10] T Bugarcic A Habtemariam J Stepankova et al ldquoThe con-trasting chemistry and cancer cell cytotoxicity of bipyridineand bipyridinediol ruthenium(II) arene complexesrdquo InorganicChemistry vol 47 no 24 pp 11470ndash11486 2008
[11] M Castellano-Castillo H Kostrhunova V Marini et al ldquoBind-ing ofmismatch repair proteinMutS tomispairedDNA adductsof intercalating ruthenium(II) arene complexesrdquo Journal ofBiological Inorganic Chemistry vol 13 no 6 pp 993ndash999 2008
[12] S J Dougan A Habtemariam S E McHale S Parsons andP J Sadler ldquoCatalytic organometallic anticancer complexesrdquoProceedings of the National Academy of Sciences of the UnitedStates of America vol 105 no 33 pp 11628ndash11633 2008
[13] S J Dougan M Melchart A Habtemariam S Parsons and PJ Sadler ldquoPhenylazo-pyridine and phenylazo-pyrazole chloridoruthenium(II) arene complexes arene loss aquation and can-cer cell cytotoxicityrdquo Inorganic Chemistry vol 45 no 26 pp10882ndash10894 2006
[14] V Ritleng P Bertani M Pfeffer C Sirlin and J HirschingerldquoOptically active ortho-metalated half-sandwich rutheniumcomplexes solid-state NMR as a convenient tool to analyzemixtures of diastereomersrdquo Inorganic Chemistry vol 40 no 20pp 5117ndash5122 2001
[15] Y Sunada Y Hayashi H Kawaguchi and K TatsumildquoAlkynethiolato and alkyneselenolato rutheniumhalf-sandwichcomplexes Synthesis structures and reactions with (1205785ndashC5H5)2Zrrdquo Inorganic Chemistry vol 40 no 27 pp 7072ndash70782001
[16] K Yamanari R Ito S Yamamoto et al ldquoCyclic tetramerscomposed of rhodium(III) iridium(III) or ruthenium(II) half-sandwich and6-purinethionesrdquo Inorganic Chemistry vol 41 no25 pp 6824ndash6830 2002
[17] F Caruso M Rossi A Benson et al ldquoRuthenium-arenecomplexes of curcumin X-ray and density functional the-ory structure synthesis and spectroscopic characterizationin vitro antitumor activity and DNA docking studies of (p-cymene)Ru(curcuminato)chlorordquo Journal of Medicinal Chem-istry vol 55 no 3 pp 1072ndash1081 2012
[18] C Gossens I Tavernelli and U Rothlisberger ldquoBinding oforganometallic ruthenium(II) anticancer compounds to nucle-obases a computational studyrdquo Journal of Physical Chemistry Avol 113 no 43 pp 11888ndash11897 2009
[19] A M Pizarro A Habtemariam and P J Sadler ldquoActiva-tion mechanisms for organometallic anticancer complexesrdquoin Medicinal Organometallic Chemistry vol 32 of Topics inOrganometallic Chemistry pp 21ndash56 Springer Berlin Ger-many 2010
[20] I Turel and J Kljun ldquoInteractions of metal ions with DNAits constituents and derivatives which may be relevant foranticancer researchrdquoCurrent Topics inMedicinal Chemistry vol11 no 21 pp 2661ndash2687 2011
[21] G Gasser I Ott and N Metzler-Nolte ldquoOrganometallic anti-cancer compoundsrdquo Journal of Medicinal Chemistry vol 54 no1 pp 3ndash25 2011
[22] K J Kilpin S Crot T Riedel J A Kitchen and P JDyson ldquoRuthenium(II) and osmium(II) 123-triazolylideneorganometallics a preliminary investigation into the biologicalactivity of rsquoclickrsquo carbene complexesrdquo Dalton Transactions vol43 no 3 pp 1443ndash1448 2014
[23] A F A Peacock S Parsons and P J Sadler ldquoTuning thehydrolytic aqueous chemistry of osmium arene complexeswith NO-chelating ligands to achieve cancer cell cytotoxicityrdquoJournal of the American Chemical Society vol 129 no 11 pp3348ndash3357 2007
[24] A F A Peacock M Melchart R J Deeth A Habtemariam SParsons and P J Sadler ldquoOsmium(II) and ruthenium(II) arenemaltolato complexes rapid hydrolysis and nucleobase bindingrdquoChemistrymdashA European Journal vol 13 no 9 pp 2601ndash26132007
[25] F Pelletier V Comte A Massard et al ldquoDevelopment ofbimetallic titanoceneminusrutheniumminusarene complexes as anti-cancer agents relationships between structural and biologicalpropertiesrdquo Journal of Medicinal Chemistry vol 53 no 19 pp6923ndash6933 2010
[26] K J Kilpin and P J Dyson ldquoEnzyme inhibition by metalcomplexes concepts strategies and applicationsrdquo ChemicalScience vol 4 no 4 pp 1410ndash1419 2013
[27] G Gasser andNMetzler-Nolte ldquoThe potential of organometal-lic complexes in medicinal chemistryrdquo Current Opinion inChemical Biology vol 16 no 1-2 pp 84ndash91 2012
[28] I Turel J Kljun F Perdih et al ldquoFirst ruthenium organometal-lic complex of antibacterial agent ofloxacin Crystal structureand interactions with DNArdquo Inorganic Chemistry vol 49 no23 pp 10750ndash10752 2010
[29] C Adamo and V Barone ldquoToward reliable density functionalmethods without adjustable parameters the PBE0 modelrdquoJournal of Chemical Physics vol 110 no 13 pp 6158ndash6170 1999
[30] A D Becke ldquoDensity-functional thermochemistry IIIThe roleof exact exchangerdquoThe Journal of Chemical Physics vol 98 no7 article 5648 1993
[31] W J Stevens M Krauss H Basch and P G Jasien ldquoRelativisticcompact effective potentials and efficient shared-exponentbasis sets for the third- fourth- and fifth-row atomsrdquoCanadianJournal of Chemistry vol 70 no 2 pp 612ndash630 1992
[32] M J Frisch GW Trucks H B Schlegel et alOfficial Gaussian09 Literature Citation Gaussian Wallingford UK 2009
[33] D J Feller ldquoThe role of databases in support of computationalchemistry calculationsrdquo Journal of Computational Chemistryvol 17 no 13 pp 1571ndash1586 1996
[34] K L Schuchardt B T Didier T Elsethagen et al ldquoBasis setexchange a community database for computational sciencesrdquoJournal of Chemical Information andModeling vol 47 no 3 pp1045ndash1052 2007
[35] Y Liu C-G Liu S-L Sun G-C Yang and Y-Q QiuldquoRedox-switching second-order nonlinear optical responses ofNandNandN ruthenium complexesrdquo Computational and TheoreticalChemistry vol 979 pp 112ndash118 2012
[36] P S Liyanage R M de Silva and K M N de Silva ldquoNonlinearoptical (NLO) properties of novel organometallic complexeshigh accuracy density functional theory (DFT) calculationsrdquoJournal of Molecular Structure THEOCHEM vol 639 pp 195ndash201 2003
[37] MH Jamroz ldquoVibrational EnergyDistributionAnalysis VEDA4 ProgramrdquoWarsaw Poland 2004ndash2010 httpwwwsmmgpl
[38] M H Jamroz J C Dobrowolski and R Brzozowski ldquoVibra-tional modes of 26- 27- and 23-diisopropylnaphthalene ADFT studyrdquo Journal of Molecular Structure vol 787 no 1ndash3 pp172ndash183 2006
[39] M H Jamroz ldquoVibrational Energy Distribution Analysis(VEDA) scopes and limitationsrdquo Spectrochimica Acta AMolec-ular and Biomolecular Spectroscopy vol 114 pp 220ndash230 2013
Journal of Chemistry 15
[40] R Marchal P Carbonniere D Begue and C Pouchan ldquoStruc-tural and vibrational determination of small galliumndasharsenideclusters fromCCSD(T) andDFT calculationsrdquoChemical PhysicsLetters vol 453 no 1ndash3 pp 49ndash54 2008
[41] R Marchal P Carbonniere and C Pouchan ldquoStructural andvibrational properties prediction of Sn
119899Te119899clusters (n = 2ndash
8) using the GSAM approachrdquo Computational and TheoreticalChemistry vol 990 pp 100ndash105 2012
[42] T Helgaker M Jaszunski and M Pecul ldquoThe quantum-chemical calculation of NMR indirect spin-spin coupling con-stantsrdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 53 no 4 pp 249ndash268 2008
[43] F A Perras andD L Bryce ldquoTheoretical study of homonuclear Jcoupling between quadrupolar spins single-crystal DOR andJ-resolved NMRrdquo Journal of Magnetic Resonance vol 242 pp23ndash32 2014
[44] I D Burns A F Hill A J P White D J Williams and J DE T Wilton-Ely ldquoPolyazolyl chelate chemistry 61 bidentatecoordination of HB(pz)
3(pz = Pyrazol-1-yl) to ruthenium and
osmium crystal structure of [RuH(CO)(PPh3)2k2-HB(pz)
3]rdquo
Organometallics vol 17 no 8 pp 1552ndash1557 1998[45] M Al-Noaimi and M A AlDamen ldquoRuthenium complexes
incorporating azoimine and 120572-diamine based ligands synthe-sis crystal structure electrochemistry and DFT calculationrdquoInorganica Chimica Acta vol 387 pp 45ndash51 2012
[46] K Nakajima Y Ando H Mano and M Kojima ldquoPhotosub-stitution reactivity crystal structures and electrochemistry ofruthenium(II) (III) complexes containing tetradentate (O
2N2
S2N2 and P
2N2) Schiff base ligandsrdquo Inorganica Chimica Acta
vol 274 no 2 pp 184ndash191 1998[47] Z-L Lu K Eichele I Warad et al ldquoSupported organometal-
lic complexes XXXVIII [1] Bis(methoxyethyldimethlphos-phine)ruthenium(II) complexes as transfer hydrogenation cat-alystsrdquo Zeitschrift fur Anorganische und Allgemeine Chemie vol629 no 7-8 pp 1308ndash1315 2003
[48] R Gaur and L Mishra ldquoSynthesis and characterization ofRu(II)ndashDMSOndashClndashchalcone complexes DNA binding nucle-ase and topoisomerase II inhibitory activityrdquo Inorganic Chem-istry vol 51 no 5 pp 3059ndash3070 2012
[49] B Cebrian-Losantos E Reisner C R Kowol et al ldquoSynthesisand reactivity of the aquation product of the antitumor complextrans-[Ru IIICI
4(indazole)
2] minusrdquo Inorganic Chemistry vol 47 no
14 pp 6513ndash6523 2008[50] B T Rasley M Rapta and R J Kulawiec ldquoDiastereoselectivity
in enolate coordination in a new class of chiral rutheniumenolate complexesrdquo Organometallics vol 15 no 13 pp 2852ndash2854 1996
[51] S David R S Perkins F R Fronczek S Kasiri S S MandalandR S Srivastava ldquoSynthesis characterization and anticanceractivity of ruthenium-pyrazole complexesrdquo Journal of InorganicBiochemistry vol 111 pp 33ndash39 2012
[52] B Dutta E Solari S Gauthier R Scopelliti and K SeverinldquoRuthenium half-sandwich complexes with sterically demand-ing cyclopentadienyl ligandsrdquo Organometallics vol 26 no 19pp 4791ndash4799 2007
[53] G Turkoglu S Tampier F Strinitz F W Heinemann E Hub-ner and N Burzlaff ldquoRuthenium carbonyl complexes bearingbis(pyrazol-1-yl)carboxylato ligandsrdquo Organometallics vol 31no 6 pp 2166ndash2174 2012
[54] A K Renfrew A D Phillips E Tapavicza R ScopellitiU Rothlisberger and P J Dyson ldquoTuning the efficacy of
ruthenium(II)-arene (RAPTA) antitumor compounds with flu-orinated arene ligandsrdquo Organometallics vol 28 no 17 pp5061ndash5071 2009
[55] P M Jeffries R E Ellenwood and G S Girolami ldquoAnionicruthenium(II) alkyls with ancillary diene and dienyl ligandssynthesis and structures of [(12057821205782-C
7H8)RuMe
4]2minus and [(12057831205782-
C8H11)RuMe
3]2minusrdquo Inorganica Chimica Acta vol 361 no 1 pp
3165ndash3170 2008[56] B R James D Dolphin T W Leung F W B Einstein
and A C Willis ldquoPreparation and characterization of someruthenium(III) porphyrins including the crystal structure ofbromo(octaethylporphinato)(triphenylphosphine)ruthenium(III)rdquoCanadian Journal of Chemistry vol 62 no 7 pp 1238ndash12451984
[57] M Plois R Wolf W Hujo and S Grimme ldquoTowards reagentsfor bimetallic activation reactions polyhydride complexes withRu2H3 Ru2ZnH6 and Cu
2Ru2H6coresrdquo European Journal of
Inorganic Chemistry vol 2013 no 17 pp 3039ndash3048 2013[58] L Hintermann L Xiao A Labonne and U Englert
ldquo[CpRu(1205786-naphthalene)]PF6as precursor in complex synthesis
and catalysis with the cyclopentadienyl-ruthenium(II) cationrdquoOrganometallics vol 28 no 19 pp 5739ndash5748 2009
[59] I W Wyman K N Robertson T S Cameron J C SwartsandM A S Aquino ldquoSynthesis structure and electrochemistryof (ferrocene-2-propenoato-OO1015840)bis[12-bis(diphenylphosphi-no)ethane-PP1015840]ruthenium(II) hexafluorophosphaterdquo Inorgan-ica Chimica Acta vol 359 no 9 pp 3092ndash3096 2006
[60] C A Vock C Scolaro A D Phillips R Scopelliti G Sava andP J Dyson ldquoSynthesis characterization and in vitro evaluationof novel ruthenium(II) 1205786-arene imidazole complexesrdquo Journalof Medicinal Chemistry vol 49 no 18 pp 5552ndash5561 2006
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 15
[40] R Marchal P Carbonniere D Begue and C Pouchan ldquoStruc-tural and vibrational determination of small galliumndasharsenideclusters fromCCSD(T) andDFT calculationsrdquoChemical PhysicsLetters vol 453 no 1ndash3 pp 49ndash54 2008
[41] R Marchal P Carbonniere and C Pouchan ldquoStructural andvibrational properties prediction of Sn
119899Te119899clusters (n = 2ndash
8) using the GSAM approachrdquo Computational and TheoreticalChemistry vol 990 pp 100ndash105 2012
[42] T Helgaker M Jaszunski and M Pecul ldquoThe quantum-chemical calculation of NMR indirect spin-spin coupling con-stantsrdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 53 no 4 pp 249ndash268 2008
[43] F A Perras andD L Bryce ldquoTheoretical study of homonuclear Jcoupling between quadrupolar spins single-crystal DOR andJ-resolved NMRrdquo Journal of Magnetic Resonance vol 242 pp23ndash32 2014
[44] I D Burns A F Hill A J P White D J Williams and J DE T Wilton-Ely ldquoPolyazolyl chelate chemistry 61 bidentatecoordination of HB(pz)
3(pz = Pyrazol-1-yl) to ruthenium and
osmium crystal structure of [RuH(CO)(PPh3)2k2-HB(pz)
3]rdquo
Organometallics vol 17 no 8 pp 1552ndash1557 1998[45] M Al-Noaimi and M A AlDamen ldquoRuthenium complexes
incorporating azoimine and 120572-diamine based ligands synthe-sis crystal structure electrochemistry and DFT calculationrdquoInorganica Chimica Acta vol 387 pp 45ndash51 2012
[46] K Nakajima Y Ando H Mano and M Kojima ldquoPhotosub-stitution reactivity crystal structures and electrochemistry ofruthenium(II) (III) complexes containing tetradentate (O
2N2
S2N2 and P
2N2) Schiff base ligandsrdquo Inorganica Chimica Acta
vol 274 no 2 pp 184ndash191 1998[47] Z-L Lu K Eichele I Warad et al ldquoSupported organometal-
lic complexes XXXVIII [1] Bis(methoxyethyldimethlphos-phine)ruthenium(II) complexes as transfer hydrogenation cat-alystsrdquo Zeitschrift fur Anorganische und Allgemeine Chemie vol629 no 7-8 pp 1308ndash1315 2003
[48] R Gaur and L Mishra ldquoSynthesis and characterization ofRu(II)ndashDMSOndashClndashchalcone complexes DNA binding nucle-ase and topoisomerase II inhibitory activityrdquo Inorganic Chem-istry vol 51 no 5 pp 3059ndash3070 2012
[49] B Cebrian-Losantos E Reisner C R Kowol et al ldquoSynthesisand reactivity of the aquation product of the antitumor complextrans-[Ru IIICI
4(indazole)
2] minusrdquo Inorganic Chemistry vol 47 no
14 pp 6513ndash6523 2008[50] B T Rasley M Rapta and R J Kulawiec ldquoDiastereoselectivity
in enolate coordination in a new class of chiral rutheniumenolate complexesrdquo Organometallics vol 15 no 13 pp 2852ndash2854 1996
[51] S David R S Perkins F R Fronczek S Kasiri S S MandalandR S Srivastava ldquoSynthesis characterization and anticanceractivity of ruthenium-pyrazole complexesrdquo Journal of InorganicBiochemistry vol 111 pp 33ndash39 2012
[52] B Dutta E Solari S Gauthier R Scopelliti and K SeverinldquoRuthenium half-sandwich complexes with sterically demand-ing cyclopentadienyl ligandsrdquo Organometallics vol 26 no 19pp 4791ndash4799 2007
[53] G Turkoglu S Tampier F Strinitz F W Heinemann E Hub-ner and N Burzlaff ldquoRuthenium carbonyl complexes bearingbis(pyrazol-1-yl)carboxylato ligandsrdquo Organometallics vol 31no 6 pp 2166ndash2174 2012
[54] A K Renfrew A D Phillips E Tapavicza R ScopellitiU Rothlisberger and P J Dyson ldquoTuning the efficacy of
ruthenium(II)-arene (RAPTA) antitumor compounds with flu-orinated arene ligandsrdquo Organometallics vol 28 no 17 pp5061ndash5071 2009
[55] P M Jeffries R E Ellenwood and G S Girolami ldquoAnionicruthenium(II) alkyls with ancillary diene and dienyl ligandssynthesis and structures of [(12057821205782-C
7H8)RuMe
4]2minus and [(12057831205782-
C8H11)RuMe
3]2minusrdquo Inorganica Chimica Acta vol 361 no 1 pp
3165ndash3170 2008[56] B R James D Dolphin T W Leung F W B Einstein
and A C Willis ldquoPreparation and characterization of someruthenium(III) porphyrins including the crystal structure ofbromo(octaethylporphinato)(triphenylphosphine)ruthenium(III)rdquoCanadian Journal of Chemistry vol 62 no 7 pp 1238ndash12451984
[57] M Plois R Wolf W Hujo and S Grimme ldquoTowards reagentsfor bimetallic activation reactions polyhydride complexes withRu2H3 Ru2ZnH6 and Cu
2Ru2H6coresrdquo European Journal of
Inorganic Chemistry vol 2013 no 17 pp 3039ndash3048 2013[58] L Hintermann L Xiao A Labonne and U Englert
ldquo[CpRu(1205786-naphthalene)]PF6as precursor in complex synthesis
and catalysis with the cyclopentadienyl-ruthenium(II) cationrdquoOrganometallics vol 28 no 19 pp 5739ndash5748 2009
[59] I W Wyman K N Robertson T S Cameron J C SwartsandM A S Aquino ldquoSynthesis structure and electrochemistryof (ferrocene-2-propenoato-OO1015840)bis[12-bis(diphenylphosphi-no)ethane-PP1015840]ruthenium(II) hexafluorophosphaterdquo Inorgan-ica Chimica Acta vol 359 no 9 pp 3092ndash3096 2006
[60] C A Vock C Scolaro A D Phillips R Scopelliti G Sava andP J Dyson ldquoSynthesis characterization and in vitro evaluationof novel ruthenium(II) 1205786-arene imidazole complexesrdquo Journalof Medicinal Chemistry vol 49 no 18 pp 5552ndash5561 2006
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
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