-~= -------. ~.. ,-.------------------.~.-.

INDIAN J. CHEM., VOL. 20A, NOVEMBER 1981

state-. A low energy band 3A(TI' F) +--- 3E(Tl' F)is expected in these complexes but it is apparentlyof too Iowan energy to be experimentally observed.Further, this may be obscured by the cationic vibra-tion expected around 4000 cm".

Nine vibrations (both IR-and Raman-active) areexpected in the far IR spectra of (NiLX2Y)- specieshaving C. symmetry". Out of these nine vibrationsfour will be stretching modes-two (Ni-X), one(Ni-Y) and one (Ni-P)-and the rest five will bedeformation modes. Only the stretching modescould be assigned unambiguously. The vNi-CIappears as a split band at ,.....312, 285, vNi-Brappears at -245,2lO; vNi-I appears at,.....200whilevNi-P appears at ,.....170 crrr-'. These assignmentshave been made after eliminating the bands due totriphenylphosphine and the cations. The presentassignments are in agreement with those reportedfor the related compounds=w?". In some cases,there appears a shoulder near the vNi-CI band, thismay be due to solid state interactions" In all thepresent complexes, the vNi-X values lie betweenthose of (NiX4)2- (Td)16 and NiL2X2 (C2V)5. Thismay be explained on the basis that successive replace-ment of negatively charged halide ions by neutralPPh3 molecules will result in an increase in theeffective positive charge on the central Ni(II) ionand hence a higher force constant for (Ni-X) bond.It may also be pointed out that the values of vNi-Xreported for (NiLX3)- (X= Cl, Br)5 (C3V) also liebetween the values for (NiX4)2- and NiL2X25,16.

On the basis of single crystal Weissenberg photo-graphs, [(C2H5)4N][NiLCI2Br] has been found to havetetragonal unit cell with a = 17.755 A and c =17.820 A. Space group could not be assigned un-ambiguously due to the lack of complete Weissenbergdata. X-ray powder photographs of other com-pounds with (C2H5)4N+ cation indicate that theseare isomorphous and nearly isodimensional with[(C2H5)4N] [NiLCI2Br].

The authors are grateful to Prof. R. C. Aggarwal(BHU, Varanasi) and Dr. UR.K. Rao (BARC,Bombay) for helping in magnetic measurementsand to Dr. S. M. Prasad (Physics Department, R.U.,Ranchi) for his help in X-ray work. One of them(A.K.) is thankful to the CSIR, New Delhi for thefinancial assistance.

References1. COLTON,R. & CANTERFORT,J. H., Halides of the first row

transition metals (Wiley interscience, New York), 1969.2. FURLANI,C. & MORPURGO,G. Zh. phys. Chem., 28 (1961),

93.3. COTTON, F. A., FAUT, O. D. & GOODGAME,D. M. L.,

J. Am. chem. Soc., 83 (1961), 344.4. GOODGAME,D. M. L. & GOODGAME,M. Inorg. Chem.,

4 (1965), 139.5. BRADBURY,J., FOREST,K. P., NUTTALL, R. H. & SHARP,

D. W. A., Spectrochim. Acta, 23A (1967), 1780.6. MUNDIE, J. H. & NUTTALL, R. H., J. inorg: nuc/. Chem.,

31 (1969), 479.7. MISHRA, M. K. & RAO, D. V. R., J. organometal. Chem.,

22 (1970), 227.8. GEARY,W. J., Coord. chem. Rev., 7 (1971), 81.9. WILKINS,R. G. & LEWIS, J., Modern coordination Chemis-

try (Interscience, New York), 1964, 403.

1124

10. GILL, N. S. & NYHOLM, R. S., J. chem. Soc., (1959),3997.

11. GOODGAME,D. M. L., GOODGAME,M. & COTTON,F. A.,J. Am. chem. Soc., 83 (1961), 4161.

12. MARCOTRIGIANO,G., MENABUE& PELLACANI,C., Inorg.chim. Acta, 26 (1978), 57.

13. JHA, N. K. & SAXENA,A., J. inorg . nucl. Chem., 48 (1978),1601.

14. GARRETT,B. B., GOEDKEN,V. L. & QUAGLIANO,J. V., J.Am. chem. Soc., 92 (1970), 489.

15. NAKAMOto, K., Infrared and Raman spectra 0/ inorganicand coordination compounds (Wiley Interscience, NewYork), 1977, 146.

16. SABATINI,A. & SACCONI,L., J. Am. chem, Soc., 86 (1964),17.

17. BOORMAN,P. M. & CARTY,A. J., Inorg . nucl. chem. Lett.,4 (1968), 101.

Interaction of Nitrosyl Chloride, Bromide, Nitrite &of Nitrosyl Tribromide with Ruthenium Complexes

K. C. JAIN, K. K. PANDEY& U. C. AGARWALA*Department of Chemistry, Indian Institute of Technology,

Kanpur 208 016

Received 31 March 1981; revised and accepted 15 May 1981

The reactions of Ru(CO). (PPh3). and RuHCI (CO) (PPh3)3

with NOCI, NOBr, NOBr3 and dinitrogen .trioxide or NONO.are described. The products have been characterized by elemen-tal analyses, IR, conductivity and magnetic data.

DURING the course of reactions of NOX (X=CI, Br, Br3, N02) with transition metal halides

in the presence of triphenylphosphine and withtransition metal complexes.v", it was found thatthese electrophiles can be used as a good nitrosyla-ting agent. In this note we report the syntheses ofcompounds formed as a result of the interaction ofNOX with Ru(CO)3 (PPh3)2 and RuHCl(CO)(PPh3)3'

NOX (X = Cl, Br, Br3 and N02), Ru(CO)J (PPh3)2and RuHCI(CO)(PPh3)3 were prepared by the lite-rature method=w. Infrared spectra of the complexes(vmax in crrr'<) were recorded in KBr in the range4000-250 crrr-' on a Perkin-Elmer model-580.

(1) Reactions of NOCI with Ru(CO)g(PPh3)2 andRu(CO)HCI(PPh3)3 - A solution (20 ml) of NOCIin CH2Cl2 was added to a solution (lO ml) ofRu(CO)3(PPh3)2 (0.5 g) in dichloromethane and to this wasadded hot methanol (40 ml). On vigorous stirringorange glistening crystals of Ru(NO)Cla(PPh3)2(yield, 80%; m.p. 240-42°) separated out which werecentrifuged immediately, washed with methanol,ether and dried in vacuo (vNO at 1876). On keep-ing the centrifugate for 3-4 hr a white compoundseparated out which was centrifuged washed withmethanol, ether and dried in vacuo (yield 10%;vCO, 2064, 2001; m.p. 259-60°). The same com-pounds were obtained when RuHCI(CO)(PPh3)3 wasused as a starting material.

On changing the reaction medium from dichloro-methane to benzene, there was no change in thereaction products.

NOTES

(2) Reaction of NOBr with Ru(CO)a (PPha)2 orRuHCI(CO)(PPha)a - The procedure for the re-action was the same as that given in (1). Thereaction of Ru(CO)a (PPh3)2 gave orange plates ofRu(NO)Bra(PPha)2 (yield 30%; m.p. 228°; vNO-1874) and a white compound Ru(CO)2Br2(PPh3)2(yield 40%; m.p. 233°; vCO 2040, 1980). WhenRuHCI(CO) (PPha)a was taken as the starting materialin place of RU(CO)3 (PPh3)2' orange plates ofRu(NO)Br2CI(PPh3)2 were obtained (yield 30%;m.p. 235°; vNO 1874).

(3) Reaction of NOBr3 with Ru(CO)a (PPh3)2 orRuHCI(CO)(PPh3)a - The procedures for thereaction of NOBra with Ru(CO)aCPPha)2 andRuHCI(CO)(PPha)3 were the same as in (2). BothRu(COMPPha)2 and RuHCI(CO)(PPha)a yieldedRu(NO)BriPPha)2 (yield 20%, m.p. 228°; vNO1874) and Ru(CO)2BriPPha)2 (yield 50%; m.p.233°; vCO 2040, 1980).

(4) Reaction of N20a with Ru( cOMP Pha)2 andRuHC/ (CO) (PPh3)3 - A saturated solution (20 ml)ofNON02 in CH2Cl2was added to a solution (10 ml)of RU(CO)3 (PPh3)2 (0.5 g) in CH2CI2. The reactionmixture was concentrated on a water-bath and hotmethanol (50 ml) added to it. On keeping the reac-tion mixture overnight a yellow compound was ob-tained which was contrifuged, washed with methanol,ether and dried in vacuo (m.p. 171-720).

The characterisation data of the complexes aregiven in Table 1. All the complexes' are stable inair, partly soluble in chloroform, dichloromethaneand benzene. The conductivity of all the complexesin nitrobenzene (10-3 M solutions) were very low(sp. condo p. = 4 to 7 ohnr-' em" mol") which rulesout the ionic character of the complexes.

The position of vNO band ('" 1874) suggeststhat NO is coordinated as NO+ in the nitrosyl comp-lexes+. The presence of PPha and carbonyl group

is indicated by their characteristic IR bands. Thusassuming NO acting as NO+, ruthenium in thesecomplexes should be present in +2 oxidation statewhich is further corroborated by their diamagneticbehaviour.

It will be interesting to observe that the percentageyields ofthe nitrosyl complexes vary with the stabilityof NOX in CH2Cl2 (NOCI > NOBr > NOBra)6-8

while that of the dicarbonyl complexes in the reverseorder. It could possibly be related to the time forwhich NO remains in solution.

Generally the trans Ru (CO)2X2(PPh3)2 are paleyellow to yellow coloured-v-" while the cis-isomersare colourless and relatively more stable. Since thecolour of dicarbonyl complexes prepared is white,it is tacitly presumed that RU(CO)2 CI2(PPh3)2 shouldbe having more stable cis-configuration (I). The cis-geometry is supported by the m.p. (259-60°) and thepositions of vCO bands (2004 and 2001) of RU(CO)2CI2(PPh)3' which correspond to those preparedearlier by other method-s.

The melting point (233°) and the positions of thev CO bands (2040, 1980 and a shoulder at 1958)of the white complex Ru(CO)2Br2(PPha)2 differfrom those reported for cis-RuBr2(COMPPh3)2.15

It is assumed that the present complex does nothave the cis-geometry as shown in structure (II).Consequently anyone of the remaining two cis-geometries (III or IV)16 could possibly be assignedto Ru(CO)2Br2(PPh3)2 :

CO coCO I PPh3 co \ PPh3<, / <, /

Ru Ru/ \ <, / \ <,

Ph3P R ci PPh.R Cl

I, R = Cl (UT)II R = Br

ClCO \ PPhs

""- /Ru

/1""-co 1 PPh3

Cltry)

..Products

TABLE 1- CHARACTERISATION DATA OF THE COMPLEXES

Found (%) (Calc.)

3.7(3.5)

M, = Ru(COMPPh3).; M. = RuHCl(CO)(PPh3)3' X = Ru(CO). Br, (PPhs)2; Y = Ru(NO)Br3(PPh3).

Method Starting material

Ml or M. + NOCI Ru(NO)ClaCPPh3).

+Ru( CO).Cl.(PPh3)2

2 Ml + NOBr X+y

M2 + NOBr Ru(NO)ClBr. (PPh3) + X

3

4

M, or M. + NOBr3

M, or M. + N203

X+YRU(N02)(N03)(CO).(PPh3).

C H

56.5 4.0(56.1) (3.9)

60.7 3.9(60.6) (4.0)54.3 3.8

(54.2) (3.6)48.1 3.5(48.3) (3.3)50.6 3.4

(50.7) (3.5)

51.3 3.5(51.8) (3.8)

N

2.1(1.8)

1.5(1.6)1.5

(1.6)

Cl/Br* Pt

14.2 7.9(13.9) (8.1)

9.1 8.0(9.4) (8.2)19.2 1.5

(19.0) (7.4)26.5 7.0(26.8) (6.9)22.6 7.0

(22.9) (7.2)

7.6(1.8)

*Halides were estimated as usual" after decomposing the complex with KOH and NaN03•

tPhosphorus was estimated as phosphoammonium molybdate after decomposing the complex with Na.O., sugar andNaN03 in a Parr bomb.

1125

INDIAN J. CHEM., VOL. 20A, NOVEMBER 1981

Interaction of NON02 with RU(CO)3 (PPh3)2 orRuHCI(CO)(PPh3)3 affords N-bonded nitro-nitratecomplex Ru(N02) (N03)(CO)2 (PPh3)2 as indicatedby the characteristic NO; bands (1390, 1317, 825)and NO; bands (1494, 1270, 995). A small peak at1873 is in the IR spectrum of the above compoundindicates the presence of Ru(NO)(N03MPPh3)2 asan impurity. Formation of the NO; ligand as N-bonded rather than O-bonded is supported by thepresence of the characteristic band of N-bondedNO; in the region of 1317 (ref. 17-19).

It is interesting to point out that the reaction ofNOBr with RU(CO)3 (PPh3h and RuHCI(CO)(PPh3)3gives a mixed halide nitrosyl RuBr2CI(NO)(PPh3)2while that of NOBr3 yields RuBr3(NO)(PPh3)2'

References1. JAIN, K. c., PANDEY,K. K., PARASHAD,R., SINGH, T. &

AGARWALA,U. C., Indian J. Chem., 19A (1980), 1089.2. JAIN, K. C., PANDEY,K. K. & AGARWALA,U. c., Z. anorg •

allg. Chem., 472 (1981), 217.3. PANDEY,K. K., DATTA,S. & AGARWALA,U. C., Transition

met. Chem.,4 (1979), 237.4. PANDEY, K. K. & AGARWALA,U. C., J. inorg. nucl.

Chem., 42 (1980), 293.5. PANDEY, K. K. & AGARWALA, U. C., Z. anorg . aI/g.

Chem., 457 (1979), 235.6. Shell Internat. Research Maatschappij, N. V. Nath Appl.,

6512601 (CI, COI b), 31 (1967).7. BURN, W. G. & BERNSTERIN,H. J., J. chem. Phys., 18

(1950), 1699.8. DATTA, R. L. & CHATTERJEE,N. R., J. Am. chem, Soc.,

45 (1923), 481.9. BRAUER,G., Hand book of preparative inorganic chemistry,

Vol. 1, (Academic Press, New York), (1963), 488.10. AHMAD, N., LEVISON,J. J., ROBINSON,S. D. & UTTLEY,

M. F., Inorg . synthesis, Vol. 15 p. 50.11. VOGEL, A. I., A text book of quantitative inorganic ana-

lyses, (Longmans Green, London), 1978.12. HAYMORE,B.L. & IBERS,J. I., Inorg, Chem., 14(1975), 3060.13. JOHN PETER, Chern. Ber., 103 (1970), 2118.14. WALTER, HIEBER & JOHN PETER, Chern. Ber., 103 (1970),

2161.15. JAMES, B. R. & MARKHAM, L. D., Inorg. nucl. chem.

u«, 7 (1971), 373.16. COTTON,J. D., BRUCE,M. I. & STONE,F. G. A., J. chem.

Soc. (1968), 2162.17. JAIN, P. c., LINGAFELTER,E. c., J. Am. chem. Soc., 89

(1967), 6137.18. ANDREETTI,G. D., JAIN, P. C. & LINGAFELTER, E. c.,

J. Am. chem. Soc., 91 (1969), 4112.19. BAGGIO,S. & BECKA, L. N., Acta Crystallogr., B25 (1969),

946.

Diethylenetriamine & Triethylenetetramine Adducts ofDithiophosphate & Dithiophosphinate of Nickel(II)

R. N. MUKHERJEE*& P. K. GOGorDepartment of Chemistry, Indian Institute of Technology,

Powai, Bombay 40a 076

Received 13 February 1981; revised and accepted 2 April 1981

New adducts of dithiophosphato- and dlthlophosphinato-nickel(II) with tridentate and tetradentate donors, viz, dlethy-lenetriamine and triethylenetetramine, have been synthesised andcharacterised on the basis of elemental analyses, magneticmeasurements, infrared and electronic spectral data. Withdlethylenetrlamlne both 1:1 and 1:2 adducts could be isolatedwhereas with triethylenetetramlne only 1:1 complexes could beisolated in the solid state.

1126

MAGNETIC and spectroscopic studies on penta-and hexa-coordinate complexes formed by

the expansion of the coordinatively unsaturated NiS4core in dithiophosphinato derivatives of nickel(II)through interaction with unidentate and bidentatedonors were described in our earlier papers-". Suchstudies are not available with tridentate and tetra-dentate donors such as diethylenetriamine and tri-ethylenetetramine. Complexation with these ligandsprovide different structural possibilities" and inview of this we wish to report our findings on theadducts of diethylenetriamine (dien) and triethy-lenetetramine (trien) with bisfdimethyldithiophos-phato) nickel(II), Ni(Me2dtp)2 and the correspondingdi-[(chloromethylphenyl)-dithiophosphinato] analo-gue, Ni(MeCldtpi)2'

All the chemicals used were of AR grade. Thedithiophosphinic acid and Ni(Me2dtp h were synthe-sised by methods reported elsewhere+". The electronicspectra were recorded on a Perkin-Elmer 402 andCarl Zeiss (Jena, model VSU2-P) spectrophoto-meters. Magnetic measurements were carried outon a Gouy balance using Hg [CO(SCN)4] as cali-brant. Conductivity measurements were carried outin water on a Systronics (model 305) conductancebridge at room temperature. The analytical datafor the complexes are given in Table 1.

Interaction of dien with Ni(MeCldtpi)2 resulted inthe formation of a 1: 1 light green adduct having amagnetic moment of 3.01 B. M. This is suggestiveof an octahedral stereochemistry for 1: 1 adduct.The electronic spectrum] showed absorptions at14090(43) and 20400(32) of which the band at14090 was assigned to 3A2U -+ 3T}u (F) transitionand this points to the presence of NiS4N2 or NiS3N3chromophore on the basis of earlier results onNiS4N2 chrornophores''. The former chromophorewould require dien to act as a bidentate ligands, butreported structural results=" favour a tridentatechelation for dien, hence it is more resonable toexpect NiS3N3 chromophore with un identate andbidentate dithio-ligands. The bluish green complexNi (MezdtpMdien) with a magnetic moment of 2.87B. M., showed absorption at 14280 (31), 16390 (sh)and 26180 (28) in its electronic spectrum. The shiftof the 3A 2g -+ 3T1y (F) transition to 14280 is consis-tent with the higher position of dithiophosphate inthe spectrochemical series.

Excess addition of dien produced pink 1:2 com-plexes with Ni(MeCldtpi)2 and Ni(Me2dtp)2' Thereflectance spectra showed absorptions at 11700,18180,21740 and 11730,18670,22980 respectively.It appears that the first spin allowed transition whichcould not be observed for the 1: 1 compounds dueto limitations of the instrument is now shifted to11700-11730 while the 3A2g -+ 3T]g (F) transitionis observed above 18000 crrr-'. The magnetic mo-ments were found to be 2.65 and 2.71 B. M., res-pectively. Spectral features and conductivitymeasurement (141.58 Q) for Ni(Me2dtp)2 (dien),

tElectronic absorption band (positions with molar extinctioncoefficients within parentheses) and IR vmax are expressed incm? throughout this note.