Supporting Information © Wiley-VCH 2006

69451 Weinheim, Germany

1

A Supramolecular Photocatalyst for the Production of Hydrogen and the Selective

Hydrogenation of Tolane

Sven Raua*, Bernhard Schäfera, Manfred Rudolpha, Manfred Friedricha, Helmar Görlsa

Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University, 07743 Jena,

Germany

Lessingstraße 8, 07745 Jena,

Tel.: (+49)-03641-948113

Fax.: (+49)-03641-948102

e-mail: sven.rau@uni-jena.de

Dieter Gleichb, Ernst Andersb

Institute of Organic and Macromolecular Chemistry, Friedrich Schiller University, 07743

Jena, Germany

William Henryc, Johannes G. Vosc

National Centre for Sensor Research, School of Chemical Sciences, Dublin City University,

Dublin 9, Ireland

General data

If not stated otherwise, all reactions were carried out under argon in standard Schlenk-

equipments. The solvents were freshly distilled and, if necessary, dried according to standard

methods. 4,4’-di-tert.-butyl-2,2’-bipyridin (tbbpy) [1], (tbbpy)2RuCl2 [2],

[(tbbpy)2Ru(bpym)](PF6)2 [2], tetrapyridophenazine [3] were produced according to literature

methods. All other reagents were purchased at Aldrich and used without further purification.

The mass spectra were recorded using a SSQ 170, Finigan Mat at the Friedrich Schiller

University Jena. Electrospray-Mass spectra were recorded on a Finnnigan MAT, MAT 95 XL.

2

The positive ES mass spectra were obtained with voltages of 3-4kV applied to the

electrospray needle.

Syntheses

[(tbbpy)2Ru(tpphz)PdCl2](PF6)2 (1)

A suspension of 0.3 g (0.23 mmol) 2 and 57 mg (0,22 mmol) Pd(CH3CN)2Cl2 in 130 ml

CH2Cl2 was boiled for 6 hours at reflux. After allowing the solution to cool to room

temperature, the solution was filtered, and the solvent was removed under reduced pressure.

The reddish brown reaction product was washed with 2 ml CH2Cl2 and dried under reduced

pressure. Yield: 0.3 g (88%).

M(C60H60N10RuPdCl2P2F12) = 1489,5 g/mol

1H-NMR (CD3CN, d = 1.94, T = 300K, [ppm]): d = 1.36 (CH3-tertbutyl, 18H, s); 1.48 (CH3-tertbutyl, 18H, s); 7.27 (H5, 2H, d(lc)); 7.79 (H6, 2H, d); 8.51 (H3, 2H, s(lc)); 7.50 (H5’, 2H,

d(lc)); 7.73 (H6’, 2H, d); 8.56 (H3’, 2H, s(lc)); 8.18 (phen-Pd, 2H, dd); 9.27 (phen-Pd, 2H,

d(lc)); 9.68 (phen-Pd, 2H, d(lc)); 8.06 (phen-Ru, 2H, dd); 8.31 (phen-Ru, 2H, d(lc)); 9.90

(phen-Ru, 2H, d(lc));

13C-NMR (CD3CN, d in ppm): 163.595, 163.071, 158.063, 157.291, 155.155, 153.762,

152.804, 152.518, 151.964, 148.758, 142.684, 138.686, 137.515, 135.185, 131.152, 128.701,

128.538, 128.346, 125.997, 125.528, 122.446, 122.118, 36.297, 36.133, 30.447, 30.365.

M(C60H60N10RuPdCl2P2F12) = 1489,5 g/mol

MS(ESI, THF): m/z = 1344,9 ([M-(PF6)]+, 94%); m/z = 599,8 ([M-2(PF6)]2+, 80%);

MS(ESI, CHCl3/MeOH): m/z = 1360,9 ([M-(PF6)+H2O]+, 40%); MS(ESI, CH2Cl2/MeOH,

BS227, 29-Oct-04, m1043/04): m/z = 1362,3 ([M-(PF6)+H2O]+, 35%), m/z = 1343,2 ([M-

(PF6)]+, 70%);

MS(FAB, nba) m/z = 1344 (M-PF6);

3

[(tbbpy)2Ru(tpphz)](PF6)2 (complex 2)

The tpphz-ligand (2.3 g, 6 mmol) was partly dissolved in boiling ethylene glycol (1 l) by

means of microwave irradiation. Afterwards, a solution of [(tbbpy)2RuCl2] (1.43 g, 2 mmol)

in ethylene glycol/aceton (60 ml/4 ml) was slowly added dropwise within 6 h under further

microwave irradiation. Then, the solvent was distilled off to 20 ml. After allowing the

solution to cool to room temperature,, it was filtered off from the unconverted tpphz. The

solid was washed with ethanol (80ml). The ethanol of the combined filtrates was removed and

the remaining solution purified by column chromatography (silica gel, ethanol). The red band

remaining on the column was washed off with ethanol/KNO3(aq) (9:1), the solvent removed

under reduced pressure and the remaining aqueous solution extracted with CH2Cl2. The

resulting product consisted of 10-15 % [(tbbpy)2Ru(tpphz)Ru(tbbpy)2](PF6)4 and 85-90 %

[(tbbpy)2Ru(tpphz)](PF6)2 (1). Complex 1 was obtained by fractional crystallization from

acetonitrile/toluene. Yield: 75 %. Crystals for the x-ray structural analysis were grown from a

mixture of toluene/acetone.

M(C60H60N10RuP2F12) = 1312 g/mol

1H-NMR (d3-CD3CN, d = 1,93 ppm, T = 300K, [ppm]): d = 1.34 (CH3-tert.butyl, 18H, s); 1.47

(CH3-tert.butyl, 18H, s); 7.27 (H5, 2H, d(lc)); 7.75 (H6, 2H, d); 8.50 (H3, 2H, s(lc)); 7.51 (H5’,

2H, d(lc)); 7.75 (H6’, 2H, d); 8.55 (H3’, 2H, s(lc)); 7.88 (phen-free, 2H, dd); 8.91 (phen-free,

2H, d(lc)); 9.74 (phen-frei, 2H, d(lc)); 7.96 (phen-Ru, 2H, dd); 8.22 (phen-Ru 2H, d(lc)); 9.65

(phen-Ru, 2H, d(lc)); 13C-NMR (CD3CN, [ppm]): d = 30.449, 30.563, 30.881, 36.218, 36.410, 122.242, 122.478,

125.600, 125.645, 125.971, 126.775, 127.935, 129.988, 139.108, 141.111, 148.194, 150.889,

152.146, 153.279, 153.999, 157.434, 158.272, 163.278, 163.721;

MS(ESI, MeOH): m/z = 1167,4 ([M-(PF6)]+); m/z = 511,2 ([M-2(PF6)]2+).

4

[[(tbbpy)2Ru]2(tpphz)](PF6)2 (Complex 3)

For synthesizing the compound, 2 (0,3g, 288,6 mmol) was suspended with [(tbbpy)2RuCl2]

(0,162 g, 288,6 mmol) in 60 ml ethanol and 40 ml water, and boiled in the microwave for 90

minutes with 200 W at reflux. After adding 0,15 g NH4PF6, the solvent was removed under

reduced pressure, the red precipitate was collected on a G3-frit, washed with pentane and

dried. Yield: 96%. Crystals for the x-ray structural investigation were grown from a mixture

of toluene/acetone.

M(C96H108N14Ru2P4F24) = 2240 g/mol

1H-NMR (d3-CD3CN, d = 1,931 ppm, T = 300K, [ppm]): d = 1.349 (CH3-tertbutyl, 36H, s);

1.456 (CH3-tertbutyl, 36H, s); 7.231 (H5, 4H, d(lc), 3J = 6,4 Hz, 4J = 2 Hz); 7.489 (H5’, 4H,

d(lc), 3J = 6,4 Hz, 4J = 2 Hz); 7,598 (H6, 4H, d, 3J = 6 Hz); 7,702 (H6’, 4H, d, 3J = 6 Hz);

8,006 (Hm, 4H, dd); 8,251 (Ho, 4H, d(lc), 3J = 5,2 Hz, 4J = 1,2 Hz); 8,496 (H3, 4H, s); 8.541

(H3’, 4H, s(lc), 4J = 2 Hz); 13C-NMR (CD3CN, [ppm]): d = 163,90; 163,76; 158,09; 157,85; 155,25(C-Ho); 152,49(C-

H6’); 152,11(C-H6); 151,75; 141,58; 134,61 (C-Hp); 131,06; 128,51(C-Hm); 125,75 (C-H5’);

125,55 (C-H5); 122,64 (C-H3’); 122,56(C-H3); 30,56 (C-tert.butyl); 30,47 (C-tert.butyl);

MS(ESI, MeOH): m/z = 2095,5 ([M-(PF6)]+, 20%); m/z = 975,2 ([M-2(PF6)]2+, 40%);

[(tbbpy)2Ru(bpym)PdCl2](PF6)2 (4)

100 mg (0,09 mmol) [Ru(tbbpy)2(bpm)](PF6)2 were heated with 28 mg (0,11 mmol)

PdCl2ACN2 (1,2 equivalents) in acetonitrile for 5 hours under reflux. In this process, the

colour of the solution changed from red to dark green. After filtering the solution, the solvent

was removed by distillation. The raw product was recrystallized from toluene/acetonitrile.

Yield: 95%.

5

1H-NMR [CD3CN in ppm] : 9,2 (dd, 2H); 8,484 (s,4H); 8,181 (dd, 2H); 7,967 (d, 2H); 7,765

(t,2H); 7,391 (m, 6H); 1,319 (d, 36H)

MS (ESI, MeOH) (m/z): 1118,7 [M-(PF6)]+, 20%; 972 [M-2(PF6)]+

Experiments Concerning the H2-development

a) Reaction Conditions

These experiments were carried out in a submerged Schlenk-reactor which was specially

developed for this purpose. The temperature control of the set-up took place in a water bath

which was connected to a cryostat. In this way, the internal temperature could be maintained

at 25±1 °C, controllable with an internal thermometer. An LED-torch served as the radiation

source.

For executing the experiments, the submerged Schlenk-reactor was filled with the catalyst and

evacuated and filled with argon. Afterwards, dry and oxygen-free acetonitrile and TEA were

added, and the neck for sampling was closed with a septum fixed at the Schlenk-neck with a

wire. The reaction vessel was positioned in the water bath and equipped with the LED-stick.

After starting the magnetic stirrer and checking the temperature, the LED-torch was switched

on. In certain time intervals gas samples with a volume of 0,5 ml were taken and analyzed by

means of GC-analysis.

b) The Reactor

The submerged Schlenk-reactor developed for this purpose has an external diameter of ca. 3,5

cm. The immersion mantle, which is about 21 cm long and has an external diameter of ca. 2,5

cm and a 29/32-NS-core, can be introduced into the reactor’s Schlenk-neck which consist of a

29/32-NS-socket. Two further necks facilitate temperature checks by means of an internal

thermometer as well as the extraction of gas samples via a septum.

c) The LED-Torch

The LED-torch consists of a stick-shaped printed board (length 19 cm, breadth 1 cm). At its

end, 30 LEDs (manufacturer: Kingbright, type L-7113PBC-Gblue, light emission: 470±20

nm, luminous efficiency: 2000 mcd per LED) are soldered on front- and backside in a range

of 9 cm. The torch can be placed within the immersion mantle of the Schlenk-reactor.

6

Abb. 1 Equipment for the examination of the photocatalysis; on the left the submerged

reactor, on the right the LED-torch

Time Course of the Hydrogen Production

ccomplex = 5,2 x 10-5 mol/l, solvent: acetonitrile, cTEA = 2,08 mol/l

7

Hydrogenation of Tolane

Diphenylacetylene (0,24 g, 1,35 mmol) was weighed in under air and filled in a Schlenk-

vessel. After evacuating and refilling with argon, a stock solution of 1 containing 2,7 µmol 1

was added. Afterwards, the reactor was filled up with a 2 M solution of triethylamine in

acetonitrile. The resulting volume of 52 ml provided the suitable depth of immersion for the

thermometer. As an internal standard, 0,24 g diethylene glycol-di(n-butyl)ether were finally

added to the solution with a syringe. Then, the Schlenk-vessel was closed and irradiated with

the LED-torch. The formation of hydrogen was investigated by taking a gas sample of 0,5 ml

which was injected into a gas phase-chromatograph. In case of dark reactions, the reaction

vessel was wrapped in aluminium foil and thus protected from light. The reaction solution

was measured immediately after the end of the reaction.

Calibration Curve for Hydrogen

In order to create a calibration curve for hydrogen, varying volumes of H2 (VH2 = 0,5 ml, 1 ml,

2,5 ml, 5 ml und 10ml) were given into a Schlenk-vessel filled with argon (V = 0,51 l),

adjusted to the ambient pressure and mixed. Three times in succession, a gas sample from the

Schlenk-vessel (V= 0,5 ml) was analysed by means of GC.

The amount of hydrogen in the gas samples of 0,5 ml is already known, this value was

correlated to the peak area ascertained by the TCD. From the calibration curve determined in

this way the whole amount of hydrogen in the gas phase can be calculated.

Selective Hydrogenation of Tolane under Addition of Hydrogen

Diphenylacetylene (0,24 g, 1,35 mmol) was weighed in the air and filled in a Schlenk-vessel.

After evacuating and refilling with argon, a volume of a stock solution of 1, containing 2,7

µmol of the catalyst, was added. Then, the reactor was filled up with acetonitrile. The

resulting volume of 52 ml provided the suitable depth of immersion for the thermometer.

Finally, 0,24 g diethylene glycol-di(n-butyl)ether were taken off with a syringe and added to

the solution. The weight of the standard was precisely determined by differential weighing.

Afterwards, the argon gas phase was substituted by hydrogen. For that, the gas phase was

removed with a pump for three times, and then hydrogen was introduced with 0,4 mbar excess

pressure. After the end of the reaction, samples of the solution were measured by means of

gas chromatography.

8

[1] Rau S., Ruben M., Büttner T., Temme C., Dautz S., Görls H., Rudolph M., Walther

D., Brodkorb A., Duati M., O'Connor C., Vos J.G.; Dalton Trans. (20) 3649-3657

2000

[2] Rau S., Schäfer B., Grüssing A., Schebesta S., Lamm K., Vieth J., Görls H., Walther

D., Rudolph M., Grummt U.W., Birkner E.; Inorg. Chim. Acta 357 (15) 4496-4503

2004

[3] Chiorboli C., Rodgers M.A.J., Scandola F.; J. Am. Chem. Soc. 125, 483-491; 2003

Analytics

Gas-chromatographic Methods

The gas-chromatographic examinations were carried out with a chromatograph of type CP

9000 (manufacturer: CHROMPACK). Nitrogen was employed as a carrier gas, and an FID

functioned as a detector. The samples from hydrogenation reactions were analyzed on a

column with a length of 10 m, a layer thickness of df = 0,12 µm and a pressure of 50 kPa. The

column material was CPSIL 5 cb. Temperature program for the analysis of samples from

catalytic reactions: 40 °C: 2 min isothermal, heating rate: 20 °C/min, final temperature: 300

°C.

Retention times: diethylene glycol-di(n-butyl)ether, tR = 9,9 min; cis-stilbene, tR = 10,6 min;

tolane, tR = 11,4 min; trans-stilbene, tR = 11,8 min.

For the analysis of the H2-gas samples, a gas chromatograph (manufacturer: Hewlett Packard,

Series II 5890) with a thermal conductivity detector and a CHROMPACK-column (molecular

sieve 5 Å, 25 m × 0.32 mm) were used (tR H2: 2.5 min).

For GC-MS-investigations, helium functioned as carrier gas, and the mass spectrometer of

type MAZ 95 XL was employed. Columns of type CP-Sil-5 with an internal diameter of

dinternal = 0,25 mm were used for all gas-chromatographic measurements.

EPR-Measurements

The EPR-measurements were executed at a Bruker ESP 300 spectrometer in the X-band. The

irradiation of the samples in the cavity of the spectrometer ensued by means of a high-

pressure mercury vapour lamp via an HgMon 436 nm filter (irradiation equipment BUV,

ZWG Berlin). The samples – a solution of the complex (c = 2,5 E-04 mol/l), TEA (c = 14,4 E-

9

3 mol/l) in methylene chloride – were measured in a flat cell which was 4 cm long, 1 cm

broad and 0,1 cm thick.

EPR-spectrum of the Photoreduced Species

Electrochemistry

The electrochemical measurements were executed at a PGSTAT booth (manufacturer:

Autolab) by aid of the appropriate GPES software. The experiments were carried out by

means of three-electrode technique in degassed acetonitrile with

tetrabutylammoniumtetrafluoroborate (c = 0,1 mol/l) as conducting salt. An Hg-dropping

electrode or a rotating-disc-platinum electrode was used as working electrode. The reference

electrode was an Ag/AgCl-electrode. Further electrochemical measurements were executed

with a computer-controlled home-built instrument based on the DAP-3200a Data Acquisition

Board (DATALOG Systems). All experiments were carried out by means of three-electrode

technique. Acetonitrile, to which 0,25 M tetrabutylammoniumhexafluorophosphate were

added, served as a solvent. The electrolyte resistance which had to be compensated was

determined with impedance measurements of the basic electrolyte. To this end, the working

potential for the impedance measurement was chosen in a way that no electrochemical

processes took place at the compound which was to be examined. The background current

adjustment was carried out by subtracting the current curves of the pure electrolyte (with the

same concentration of supporting electrolyte). An Ag/AgCl-electrode in acetonitrile with a

concentration of 0,25 M tetrabutylammoniumchloride was the reference electrode. The

electrode’s calibration took place according to the ferrocene standard potential in acetonitrile

for which a value of +0,827 V was assumed. A platinum electrode with a diameter of 1,5 mm

10

(Bioanalytical Systems, Inc., West Lafayette, USA) served as the working electrode. The

concentration of the complexes measured was 1 mmol / l.

Representative CV examinations at 1

Cyclovoltammogram of the reduction of 1. The red circle marks an irreversible reduction

which was assigned to the Pd-reduction.

(vs. Ag/AgCl, E(Fc/Fc+ = +0,827 V), with feeding rates of 100, 200, 400 and 800 mV/s;

Ered: -0,59 V; 0,78 V (peak potential of the palladium reduction); 1,05 V; 1,24 V; 1,39 V)

UV-vis-spectroscopy

The recording of the UV-vis-spectra took place either at a double-beam instrument (Cary 1,

manufacturer: VARIAN) or at a single-beam instrument (Specord S 600, manufacturer:

Analytikjena), with the standard software WinASPECT. For measuring, HELMA QF 110

cuvettes were used (material: quartz, layer thickness: 10 mm, closable with a septum). The

respective solvent of the sample served as a reference.

Luminescence Spectroscopy

Emission spectra were recorded with an LS50B, manufactured by PERKIN-ELMER (slit

width: 10 nm; scan rate: 100-500 nm/min), by aid of the software version 3.0. If necessary,

measurements were executed ten times in order to optimize the signal-noise-ratio.

800

600

400

200

0

-200

-400

-0.5 -0.75 -1 -1.25 -1.5E(V):

I/µA

-0,5 -1 -1,5U / V

11

Emission Lifetime Measurements. Luminescence lifetime measurements were obtained

using an Edinburgh Analytical Instruments (EAI) time-correlated single-photon counting

apparatus (TCSPC) comprised of two model J-yA monochromators (emission and excitation),

a single photon photomultiplier detection system model 5300, and a F900 nanosecond

flashlamp (N2 filled at 1.1 atm pressure, 40 kHz or 0.3 atm pressure, 20 kHz) interfaced with

a personal computer via a Norland MCA card. A 410 nm cut off filter was used in emission to

attenuate scatter of the excitation light (337 nm); luminescence was monitored at the λmax of

the emission. Data correlation and manipulation was carried out using EAI F900 software

version 6.24. Samples were deaerated for 30 min using Argon prior to measurements followed

by repeated purging to ensure complete oxygen exclusion. Emission lifetimes were calculated

using a single-exponential fitting function, Levenberg-Marquardt algorithm with iterative

deconvolution (Edinburgh instruments F900 software). The reduced χ2 and residual plots

were used to judge the quality of the fits. Lifetimes are ± 5%.

NMR-spectroscopic Examinations Concerning the Photostability of 1 under

Photocatalytic Conditions

In order to check the photostability of complex 1, the complexes 1 und 2 were examined in a 1H-NMR-experiment. For this purpose, 0,5 ml of a solution of the respective complex (1,5

mmol/l) with triethylamine (c = 1,4 mol/l) in CD3CN (oxygen-free) were irradiated with the

LED-torch in the NMR-tube for one hour. The 1H-NMR-spectra and the H,H-cosy-spectra for

both complexes were measured before and after irradiation. The decay products of the

triethylamine are visible in the aliphatic area. By aid of the respective H,H-cosy-spectra, the

signals for 1 and 2 could be related to the two 4,4’-tert.butyl-2,2’-bipyridine-ligands and the

two coordination spheres of the tpphz-bridge ligand. This assignment was supported by

comparisons with the 1H- and the H,H-cosy-NMR-spectrum of complex 3 on the one hand

and by the NOESY-NMR-spectrum of 1 on the other hand.

The hydrogen atoms in para position to the coordinating nitrogens of the tpphz-ligand make

up a cross peak in the NOESY-NMR-spectrum. This fact facilitates an unambiguous

assignment of the hydrogen resonances of the tpphz-ligand.

The chemical shifts of the tpphz-bridge ligand’s signals are given in table 1. Here, in one

column the resonances of the Ru-coordinating tpphz-side of complex 1 and 2 are compared

with each other. In a second column, the chemical displacements of the tpphz-resonances of

that side of 1 which coordinates to the Pd are compared with those of the free coordination

sphere of 2.

12

The signal of the two ortho hydrogens adjacent to the two Pd-coordinating nitrogens is

characteristic for the coordination of the palladium at the tpphz.

In the table, the chemical displacements of these signals are displayed bold and in italics. A

dissociation of Pd from the tpphz-coordination sphere during irradiation should give rise to

the fact that the chemical shifts of the “indicative” hydrogen resonances of 1 and 2 become

very similar (table 1).

Table 1 NMR-spectroscopy of 1 and 2 in CD3CN/TEA before and after irradiation. Only

the chemical shifts of the relevant signals of the tpphz-ligands are listed

d Ru-sphere / ppm d free sphere / Pd sphere /ppm

not irradiated 9,90; 8,30; 8,06 9,68; 9,26; 8,18 1

irradiated 9,84; 8,21; 7,97 9,83; 9,20; 7,97

not irradiated 9,66; 8,22; 7,96 9,77; 8,91; 7,88 2

irradiated 9,65; 8,23; 7,97 9,74; 8,95; 7,85

The comparison of the 1H-NMR-spectra of complex 1 before and after irradiation indicates

only a slight displacement of the CH-signals in ortho position to the Pd-coordinating nitrogen

donators. This fact proves that palladium remains coordinated in spite of irradiation.

A comparison of the CH-signals in 1 and 2 was executed after irradiation. Since these signals

are especially sensitive to a Pd-coordination, a relatively big difference between the chemical

shifts (about 0,3 ppm) is visible. This fact also indicates that no palladium is split off from the

reduced complex.

Crystal-structure Analyses

The intensity data for the compounds were collected on a Nonius KappaCCD diffractometer,

using graphite-monochromated Mo-Kα radiation. Data were corrected for Lorentz and

polarization effects, but not for absorption effects [1,2].

The structures were solved by direct methods (SHELXS [3]) and refined by full-matrix least

squares techniques against Fo2 (SHELXL-97 [4]). The hydrogen atoms were included at

calculated positions with fixed thermal parameters. All nonhydrogen atoms were refined

anisotropically [4]. XP (SIEMENS Analytical X-ray Instruments, Inc.) was used for structure

representations.

13

Crystal Data for 2 [5]: C60H60F12N10P2Ru * C7H8 * 1/2 C3H6O, Mr = 1433.36 gmol-1, red-brown

prism, size 0.03 x 0.03 x 0.02 mm3, triclinic, space group P-1, a = 11.2595(2), b = 15.1007(4), c

= 22.1913(5) Å, α = 92.786(1), β = 91.895(1), γ = 105.982(1)°, V = 3618.7(1) Å3 , T= -90 °C, Z

= 2, ρcalcd. = 1.315 gcm-3, µ (Mo-Kα) = 3.38 cm-1, F(000) = 1476, 25198 reflections in h(-14/14),

k(-19/16), l(-28/27), measured in the range 1.84° ≤ Θ ≤ 27.49°, completeness Θmax = 98.4 %,

16348 independent reflections, Rint = 0.034, 12170 reflections with Fo > 4σ(Fo), 766 parameters,

0 restraints, R1obs = 0.084, wR2obs = 0.225, R1all = 0.115, wR2

all = 0.252, GOOF = 1.008, largest

difference peak and hole: 1.614 / -3.679 e Å-3.

crystal data for 3 [5]: C96H108F24N14P4Ru2 * 2 CH3CN, Mr = 2322.09 gmol-1, reddish-brown

cuboid, crystal size 0.03 x 0.03 x 0.02 mm3, monoclinic, space group C2/c, a = 35.8865(13), b =

19.7352(7), c = 22.3545(9) Å, β = 110.825(2)°, V = 14797(1) Å3 , T= -90 °C, Z = 4, ρcalcd. =

1.042 gcm-3, µ (Mo-Kα) = 3.16 cm-1, F(000) = 4760, altogether 42380 reflexes up to h(-

46/41), k(-23/25), l(-28/25) measured in the range of 2.38° ≤ Θ ≤ 27.47°, completness Θmax

= 97.6 %, 16540 independent reflections, Rint = 0.083, 9784 reflections with Fo > 4σ(Fo), 654

parameters, 0 restraints, R1obs = 0.102, wR2obs = 0.271, R1all = 0.169, wR2

all = 0.332, GOOF =

1.059, largest difference peak and hole: 1.551 / -0.698 e Å-3.

[1] COLLECT, Data Collection Software; Nonius B.V., Netherlands, 1998 [2] Z. Otwinowski & W. Minor, „Processing of X-Ray Diffraction Data Collected in

Oscillation Mode“, in Methods in Enzymology, Vol. 276, Macromolecular

Crystallography, Part A, edited by C.W. Carter & R.M. Sweet, pp. 307-326, Academic

Press 1997 [3] G.M. Sheldrick, Acta Crystallogr. Sect. A 1990, 46, 467-473 [4] G.M. Sheldrick, SHELXL-97, University of Göttingen, Germany, 1997 [5] CCDC- 267275 (2) and 296060 (3) include the full crystallographic data for this

publication. The data are freely available on the internet:

www.ccdc.cam.ac.uk/conts/retriewing.html (or can be required under the following

address in Great Britain: Cambridge Crystallographic Data Centre, 12 Union Road, GB-

Cambridge CB21EZ; Fax:(+44)1223-336-033; oder deposit@ccdc.cam.ac.uk).

Z DFT Calculations

All calculations were carried out without symmetry restrictions under default settings. For the

visualization of orbitals the program ‘Molekel’ was used.[Zf]

14

Z.1 Calculated Valence Angles [°] and Distances [Å] of [M2]2+

Ru-N1 2.121; Ru-N2 2.121; Ru-N7 2.113; Ru-N8 2.111; Ru-N9 2.111; Ru-N10 2.113;

N1-Ru-N2 78.4; N7-Ru-N8 77.7; N9-Ru-N10 77.7

Z.2 xyz-Coordinates of the Optimized Structures (Absolute Energies in Hartree)

[M1]2+ 86 scf done: -3383.631047 Ru -4.404346 -0.000131 0.000258 N -2.758657 1.239259 -0.506955 N -2.758617 -1.239741 0.506708 N 2.073594 1.291515 -0.529667 N 2.073634 -1.292242 0.528465 N 6.890791 1.231331 -0.518203 N 6.890833 -1.232323 0.515980 N -4.535124 1.019538 1.847366 N -5.909073 1.432543 -0.381060 N -5.909648 -1.432113 0.381818 N -4.536138 -1.019518 -1.846891 C -2.791764 2.480108 -1.004708 H -3.771802 2.902895 -1.181425 C -1.634138 3.206726 -1.294275 H -1.722757 4.207856 -1.696183 C -0.396994 2.635551 -1.063508 H 0.522752 3.163797 -1.275967 C -0.332919 1.334889 -0.539049 C -1.542306 0.669548 -0.270580 C -1.542287 -0.670078 0.270116 C -0.332881 -1.335518 0.538263 C -0.396918 -2.636237 1.062584 H 0.522844 -3.164560 1.274785 C -1.634046 -3.207386 1.293514 H -1.722634 -4.208571 1.695291 C -2.791690 -2.480665 1.004284 H -3.771720 -2.903417 1.181145 C 0.929250 0.655537 -0.267159 C 0.929269 -0.656214 0.266164 C 3.220425 0.664293 -0.275112 C 3.220446 -0.665065 0.273711 C 4.479203 -1.339560 0.556106 C 4.556193 -2.634768 1.096322 H 3.645288 -3.173412 1.319486 C 5.797399 -3.192592 1.331244 H 5.896938 -4.187268 1.745908

15

C 6.952113 -2.461108 1.028829 H 7.954367 -2.844456 1.191036 C 5.681311 -0.669248 0.278653 C 5.681290 0.668273 -0.280737 C 6.952032 2.460291 -1.030636 H 7.954274 2.843679 -1.192821 C 5.797295 3.191938 -1.332565 H 5.896801 4.186747 -1.746919 C 4.556107 2.634103 -1.097570 H 3.645185 3.172873 -1.320364 C 4.479159 1.338740 -0.557722 C -3.790973 0.762086 2.938063 H -3.083890 -0.051622 2.851105 C -3.910574 1.481142 4.118287 H -3.287242 1.229685 4.966575 C -4.837582 2.516931 4.178995 C -5.608780 2.791126 3.056985 H -6.331708 3.594042 3.087852 C -5.444515 2.031063 1.897553 C -6.222555 2.249041 0.662013 C -7.218351 3.219561 0.538836 H -7.463694 3.861730 1.372966 C -7.902228 3.360690 -0.661622 C -7.574498 2.522162 -1.722276 H -8.079835 2.593735 -2.676670 C -6.577885 1.574610 -1.539637 H -6.294348 0.903426 -2.338751 C -6.578230 -1.573947 1.540557 H -6.294109 -0.903005 2.339667 C -7.575302 -2.520984 1.723358 H -8.080431 -2.592381 2.677875 C -7.903733 -3.359253 0.662716 C -7.220106 -3.218356 -0.537912 H -7.465986 -3.860334 -1.372032 C -6.223861 -2.248321 -0.661264 C -5.446095 -2.030538 -1.897003 C -5.611157 -2.790265 -3.056543 H -6.334556 -3.592758 -3.087348 C -4.840151 -2.516277 -4.178732 C -3.912524 -1.481036 -4.118089 H -3.289291 -1.229777 -4.966509 C -3.792157 -0.762283 -2.937760 H -3.084567 0.050988 -2.850847 H -8.676660 4.110613 -0.765090 H -8.678509 -4.108801 0.766323 H -4.962007 -3.100856 -5.082186 Pd 8.500165 -0.000357 -0.000826 Cl 10.105325 1.537715 -0.651335 Cl 10.105431 -1.535385 0.656528 H -4.958822 3.101775 5.082359

16

[M1]+

86 scf done: -3383.882380 Ru -4.415900 -0.000185 0.000482 N -2.784435 1.256405 -0.467011 N -2.784371 -1.257040 0.466994 N 2.064788 1.303406 -0.508499 N 2.064857 -1.304300 0.507131 N 6.890330 1.242023 -0.498548 N 6.890399 -1.243195 0.495809 N -4.542891 0.923395 1.885495 N -5.895917 1.458004 -0.325342 N -5.896686 -1.457633 0.326146 N -4.543725 -0.923238 -1.884742 C -2.810038 2.511499 -0.920622 H -3.790393 2.944034 -1.075245 C -1.654240 3.245446 -1.194754 H -1.741926 4.260277 -1.559283 C -0.412578 2.656379 -0.989118 H 0.506789 3.189924 -1.190481 C -0.343232 1.348289 -0.507628 C -1.561084 0.664265 -0.247370 C -1.561052 -0.664932 0.247099 C -0.343165 -1.349073 0.506884 C -0.412445 -2.657248 0.988150 H 0.506950 -3.190882 1.189146 C -1.654083 -3.246309 1.193970 H -1.741718 -4.261214 1.558304 C -2.809914 -2.512245 0.920310 H -3.790253 -2.944750 1.075130 C 0.920108 0.665153 -0.257007 C 0.920144 -0.665986 0.255956 C 3.215205 0.660976 -0.260874 C 3.215243 -0.661929 0.259198 C 4.473605 -1.340145 0.530212 C 4.549262 -2.644883 1.049082 H 3.633715 -3.180485 1.260858 C 5.787891 -3.209806 1.275639 H 5.883392 -4.211776 1.673762 C 6.947367 -2.478422 0.987085 H 7.946412 -2.869663 1.144322 C 5.680300 -0.671109 0.266152 C 5.680263 0.669986 -0.268600 C 6.947228 2.477331 -0.989631 H 7.946252 2.868561 -1.147034 C 5.787713 3.208827 -1.277740 H 5.883158 4.210859 -1.675720 C 4.549116 2.643934 -1.050933 H 3.633539 3.179621 -1.262365

17

C 4.473532 1.339131 -0.532218 C -3.810181 0.604448 2.968227 H -3.109776 -0.209778 2.840028 C -3.930872 1.260164 4.181936 H -3.312816 0.961299 5.018225 C -4.856346 2.301605 4.290949 C -5.610867 2.644020 3.182948 H -6.329762 3.448637 3.250722 C -5.441613 1.950416 1.975927 C -6.188598 2.246380 0.753847 C -7.148788 3.263237 0.652887 H -7.367930 3.888834 1.506911 C -7.818866 3.468950 -0.539871 C -7.521171 2.648232 -1.631322 H -8.022906 2.766761 -2.582618 C -6.559427 1.664281 -1.478106 H -6.293368 1.011505 -2.298712 C -6.560188 -1.663752 1.478943 H -6.293558 -1.011382 2.299686 C -7.522604 -2.647071 1.632019 H -8.024292 -2.765508 2.583351 C -7.821030 -3.467274 0.540388 C -7.150975 -3.261697 -0.652411 H -7.370698 -3.886884 -1.506586 C -6.190083 -2.245496 -0.753213 C -5.443083 -1.949680 -1.975328 C -5.612930 -2.642874 -3.182496 H -6.332325 -3.447035 -3.250375 C -4.858343 -2.300640 -4.290512 C -3.932212 -1.259806 -4.181348 H -3.314075 -0.961112 -5.017639 C -3.810951 -0.604476 -2.967486 H -3.110014 0.209274 -2.839170 H -8.561514 4.252838 -0.622109 H -8.564228 -4.250653 0.622509 H -4.984676 -2.834190 -5.224413 Pd 8.493697 -0.000590 -0.001485 Cl 10.107977 1.555024 -0.629386 Cl 10.108213 -1.551532 0.637257 H -4.982229 2.835471 5.224730 [M1D]2+

85 scf done: -2923.365080 Ru -4.064004 -0.022571 0.009317 N -2.397106 -1.208338 0.572142 N -2.441092 1.213630 -0.573113 N 2.434918 -1.192296 0.550622 N 2.390157 1.343797 -0.616188 N 7.243711 -1.065615 0.491177

18

N 7.215364 1.383730 -0.631810 N -4.181583 -1.151870 -1.773671 N -5.545389 -1.452661 0.478109 N -5.592651 1.362224 -0.444001 N -4.199561 1.099818 1.794600 C -2.407848 -2.422317 1.132524 H -3.380231 -2.849213 1.339125 C -1.236955 -3.116517 1.447764 H -1.307226 -4.096910 1.901136 C -0.010458 -2.540138 1.176704 H 0.919248 -3.043010 1.406913 C 0.030155 -1.266672 0.586713 C -1.191382 -0.633515 0.296109 C -1.215057 0.676100 -0.312771 C -0.017050 1.346042 -0.619752 C -0.105090 2.617326 -1.209719 H 0.805387 3.148534 -1.452555 C -1.352048 3.155422 -1.465245 H -1.458415 4.132622 -1.918484 C -2.496914 2.425903 -1.134237 H -3.484777 2.821804 -1.328590 C 1.279917 -0.583903 0.270875 C 1.256434 0.701676 -0.320857 C 3.571334 -0.560428 0.259797 C 3.547855 0.746526 -0.341235 C 4.794721 1.432332 -0.655524 C 4.824685 2.707790 -1.241297 H 3.895961 3.210762 -1.472703 C 6.047829 3.292049 -1.508990 H 6.116673 4.273665 -1.959663 C 7.217478 2.598001 -1.189806 H 8.191692 3.028362 -1.387379 C 6.018932 0.800534 -0.364934 C 6.037185 -0.524703 0.243310 C 7.328355 -2.271839 1.044229 H 8.335460 -2.639878 1.212751 C 6.188842 -3.013045 1.384095 H 6.300864 -3.991763 1.832679 C 4.939997 -2.475694 1.137967 H 4.036736 -3.016443 1.386105 C 4.841923 -1.200874 0.553294 C -3.443022 -0.947671 -2.879211 H -2.752449 -0.116130 -2.843202 C -3.548308 -1.741395 -4.011951 H -2.930134 -1.531181 -4.875093 C -4.453805 -2.797776 -4.006506 C -5.218995 -3.017323 -2.868484 H -5.924864 -3.835571 -2.847517 C -5.070102 -2.182860 -1.759207 C -5.843243 -2.338809 -0.511236 C -6.820180 -3.318598 -0.325858 H -7.053047 -4.017032 -1.117284 C -7.501738 -3.396336 0.881682 C -7.191557 -2.485326 1.886317 H -7.696502 -2.505218 2.843387 C -6.212785 -1.532852 1.643339 H -5.942607 -0.806538 2.397430 C -6.271282 1.424964 -1.603771 H -5.983703 0.710303 -2.362613 C -7.282287 2.346066 -1.835442 H -7.795491 2.352718 -2.788293 C -7.613761 3.243079 -0.824982

19

C -6.919939 3.183797 0.376619 H -7.168457 3.872072 1.172177 C -5.910486 2.235347 0.550680 C -5.121894 2.100849 1.791510 C -5.288554 2.926198 2.905036 H -6.021441 3.720534 2.893374 C -4.506352 2.728624 4.035494 C -3.565956 1.703205 4.029156 H -2.933237 1.511040 4.885945 C -3.444475 0.917025 2.892754 H -2.726488 0.109546 2.847711 H -8.261328 -4.153194 1.033394 H -8.398993 3.975098 -0.967751 H -4.629040 3.364420 4.903544 Pd 8.954050 0.229832 -0.100424 Cl 10.839234 -1.043331 0.482443 H -4.562779 -3.440453 -4.871312 [M2]2+

83 scf done: -2335.816787 Ru -2.597255 -0.000025 0.000009 N -0.953201 1.202546 -0.592716 N -0.953197 -1.202614 0.592649 N 3.879299 1.258559 -0.605013 N 3.879302 -1.258617 0.604945 N 8.698586 1.225537 -0.590954 N 8.698589 -1.225548 0.590960 N -2.718686 1.154803 1.764814 N -4.100846 1.401826 -0.482035 N -4.100907 -1.401781 0.482120 N -2.718854 -1.154825 -1.764798 C -0.986369 2.406008 -1.173316 H -1.966449 2.814634 -1.380478 C 0.172705 3.111561 -1.508143 H 0.084992 4.082811 -1.977915 C 1.408957 2.557972 -1.235319 H 2.330469 3.069338 -1.479578 C 1.473614 1.294873 -0.624081 C 0.262439 0.649423 -0.315002 C 0.262441 -0.649491 0.314926 C 1.473617 -1.294946 0.623993 C 1.408962 -2.558053 1.235213 H 2.330476 -3.069423 1.479462 C 0.172712 -3.111648 1.508033 H 0.085002 -4.082909 1.977786 C -0.986364 -2.406087 1.173228 H -1.966445 -2.814711 1.380390 C 2.734833 0.637359 -0.306347

20

C 2.734834 -0.637426 0.306267 C 5.027497 0.649219 -0.312194 C 5.027499 -0.649267 0.312141 C 6.286283 -1.301521 0.625861 C 6.332526 -2.568350 1.235503 H 5.407888 -3.074450 1.478541 C 7.557826 -3.136172 1.509498 H 7.637817 -4.109255 1.977797 C 8.715142 -2.418795 1.165396 H 9.697531 -2.836225 1.367493 C 7.511717 -0.664025 0.319845 C 7.511715 0.664001 -0.319859 C 8.715137 2.418784 -1.165389 H 9.697525 2.836224 -1.367470 C 7.557819 3.136149 -1.509511 H 7.637807 4.109233 -1.977808 C 6.332520 2.568314 -1.235536 H 5.407881 3.074406 -1.478589 C 6.286281 1.301485 -0.625896 C -1.968865 0.978901 2.867510 H -1.268078 0.155679 2.839897 C -2.074461 1.791647 3.986747 H -1.446262 1.604318 4.847901 C -2.992255 2.837167 3.970074 C -3.769026 3.027528 2.834644 H -4.484005 3.837547 2.804496 C -3.619190 2.175165 1.739275 C -4.402912 2.300678 0.494459 C -5.393205 3.265196 0.299635 H -5.629241 3.973829 1.081006 C -6.083835 3.314385 -0.904193 C -5.769024 2.390644 -1.895740 H -6.280424 2.388271 -2.849573 C -4.776778 1.454632 -1.643779 H -4.502112 0.719467 -2.387667 C -4.776783 -1.454545 1.643898 H -4.501992 -0.719433 2.387793 C -5.769123 -2.390451 1.895881 H -6.280475 -2.388047 2.849740 C -6.084090 -3.314127 0.904323 C -5.393512 -3.264986 -0.299536 H -5.629665 -3.973571 -1.080915 C -4.403118 -2.300576 -0.494381 C -3.619440 -2.175115 -1.739231 C -3.769391 -3.027455 -2.834601 H -4.484429 -3.837423 -2.804428 C -2.992656 -2.837145 -3.970063 C -2.074778 -1.791698 -3.986766 H -1.446601 -1.604412 -4.847945 C -1.969066 -0.978973 -2.867524 H -1.268206 -0.155814 -2.839931 H -6.853853 4.059107 -1.063119 H -6.854187 -4.058763 1.063266 H -3.101938 -3.494168 -4.823965 H -3.101449 3.494207 4.823974

21

[M2]+

83 scf done: -2336.055405 Ru -2.589059 0.000001 -0.000009 N -0.954629 1.227593 -0.526496 N -0.954631 -1.227601 0.526459 N 3.886867 1.277636 -0.559054 N 3.886864 -1.277646 0.559034 N 8.710674 1.249338 -0.549512 N 8.710671 -1.249349 0.549513 N -2.732833 1.011487 1.838197 N -4.070852 1.429922 -0.405622 N -4.070849 -1.429910 0.405652 N -2.732888 -1.011496 -1.838206 C -0.985302 2.461639 -1.044074 H -1.967881 2.880317 -1.218640 C 0.167769 3.181007 -1.351982 H 0.077474 4.176611 -1.766479 C 1.412247 2.609387 -1.117734 H 2.330912 3.133354 -1.344158 C 1.478878 1.325136 -0.571495 C 0.267953 0.657597 -0.282170 C 0.267952 -0.657604 0.282138 C 1.478876 -1.325145 0.571465 C 1.412243 -2.609398 1.117700 H 2.330907 -3.133365 1.344126 C 0.167764 -3.181017 1.351943 H 0.077467 -4.176622 1.766437 C -0.985305 -2.461647 1.044036 H -1.967884 -2.880324 1.218601 C 2.741019 0.650580 -0.283894 C 2.741018 -0.650589 0.283870 C 5.034978 0.654237 -0.287071 C 5.034977 -0.654246 0.287056 C 6.296482 -1.318326 0.579147 C 6.338694 -2.604276 1.144421 H 5.410021 -3.112310 1.367726 C 7.562379 -3.185600 1.399971 H 7.637725 -4.174928 1.834461 C 8.721671 -2.461292 1.082125 H 9.702541 -2.889518 1.270750 C 7.523476 -0.674135 0.296513 C 7.523478 0.674124 -0.296518 C 8.721677 2.461282 -1.082124 H 9.702547 2.889508 -1.270745 C 7.562386 3.185591 -1.399974 H 7.637735 4.174918 -1.834463 C 6.338699 2.604266 -1.144429 H 5.410027 3.112301 -1.367737

22

C 6.296484 1.318316 -0.579157 C -2.005774 0.754103 2.941980 H -1.280838 -0.044230 2.852297 C -2.160842 1.444359 4.130147 H -1.545484 1.192958 4.983738 C -3.124775 2.460448 4.192712 C -3.871838 2.743080 3.066656 H -4.619561 3.523451 3.099594 C -3.664829 2.018857 1.879159 C -4.389703 2.257996 0.642410 C -5.355022 3.267202 0.477973 H -5.592123 3.926693 1.301448 C -6.000843 3.421354 -0.732266 C -5.678374 2.557296 -1.788154 H -6.164926 2.632968 -2.751498 C -4.715145 1.587800 -1.577710 H -4.431971 0.902267 -2.365244 C -4.715104 -1.587782 1.577760 H -4.431893 -0.902257 2.365288 C -5.678344 -2.557262 1.788229 H -6.164866 -2.632931 2.751587 C -6.000863 -3.421308 0.732347 C -5.355076 -3.267161 -0.477910 H -5.592215 -3.926643 -1.301381 C -4.389745 -2.257973 -0.642372 C -3.664902 -2.018846 -1.879141 C -3.871954 -2.743070 -3.066628 H -4.619689 -3.523427 -3.099543 C -3.124914 -2.460455 -4.192703 C -2.160963 -1.444385 -4.130165 H -1.545622 -1.192998 -4.983772 C -2.005852 -0.754126 -2.942006 H -1.280903 0.044195 -2.852345 H -6.744835 4.197900 -0.860383 H -6.744865 -4.197839 0.860483 H -3.282967 -3.017331 -5.108047 H -3.282795 3.017324 5.108062 Z.3 Spin Density Calculations (Mulliken- [Zg] and natural population analysis [Zh]) of [M1]+ and [M1D]2+ (solvent acetonitrile (CPCM-model [Ze])) table 2 Table 2: Spin density distribution of M1 and M1D

Npyrazine N’pyrazine Pd Cl Cl’

[M1]+ 0.27 / 0.27 0.30 / 0.29 –0.00 / –0.00 0.00 / 0.00 0.00 / 0.00

[M1D]2+ 0.00 / 0.00 0.00 / 0.00 0.81 / 0.79 0.05 / 0.05 - - - -

Z.4 Literature [Z] a) Gaussian 03, Revision C.02, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,

M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C.

Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G.

Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R.

23

Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene,

X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R.

Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W.

Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G.

Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D.

Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford,

J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L.

Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M.

Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and J. A.

Pople, Gaussian, Inc., Wallingford CT, 2004.

b) A. D. Becke, J. Chem. Phys. 1993, 98, 1372-1377.

c) R. B. Ross, J. M. Powers, T. Atashroo, W. C. Ermler, L. A. LaJohn, P. A. Christiansen, J.

Chem. Phys. 1990, 93, 2812-2824.

d) K. Raghavachari, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys. 1980, 72, 650-654.

e) M. Cossi, N. Rega, G. Scalmani, V. Barone, J. Comput. Chem. 2003, 24, 669-681.

f) http://www.cscs.ch/molekel.

g) R. S. Mulliken, J. Chem. Phys. 1955, 23, 1833-1840.

h) A. E. Reed, L. A. Curtiss, F. Weinhold, Chem. Rev. 1988, 88, 899-926.