Ruthenium(II) ammine and hydrazine complexes with [N(Ph2PQ)2]- (Q = S, Se) ligands

Article abstract of DOI:10.1021/ic000291c

Reactions of coordinatively unsaturated Ru[N(Ph₂PQ)₂]₂(PPh₃) (Q = S (1), Se (2)) with pyridine (py), SO₂, and NH₃ afford the corresponding 18e adducts Ru[N(Ph₂PQ)₂]₂(PPh₃)(L) (Q = S, L = NH₃ (5); Q = Se, L = py (3), SO₂ (4), NH₃ (6)). The molecular structures of complexes 2 and 6 are determined. The geometry around Ru in 2 is pseudo square pyramidal with PPh₃ occupying the apical position, while that in 6 is pseudooctahedral with PPh₃ and NH₃ mutually cis. The Ru-P distances in 2 and 6 are 2.2025(11) and 2.2778(11) ?, respectively. The Ru-N bond length in 6 is 2.185(3) ?. Treatment of 1 or 2 with substituted hydrazines L or NH₂OH yields the respective adducts Ru[N(Ph₂PQ)₂]₂(PPh₃)(L) (Q = S, L = NH₂NH₂ (12), t-BuNHNH₂ (14), 1-aminopiperidine (C₅H₁₀NNH₂) (15); Q = Se, L = PhCONHNH₂ (7), PhNHNH₂ (8), NH₂OH (9), t-BuNHNH₂ (10), C₅H₁₀NNH₂ (11), NH₂NH₂ (13)), which are isolated as mixtures of their trans and cis isomers. The structures of cis-14 and cis-15 are characterized by X-ray crystallography. In both molecular structures, the ruthenium adopts a pseudooctahedral arrangement with PPh₃ and hydrazine mutually cis. The Ru-N bond lengths in cis-14·CH₂Cl₂ and cis-15 are 2.152(3) and 2.101(3) ?, respectively. The Ru-N-N bond angles in cis-14·CH₂Cl₂ and cis-15 are 120.5(4) and 129.0(2)°, respectively. Treatment of 1 with hydrazine monohydrate leads to the isolation of yellow 5 and red trans-Ru[N(Ph2PS)2]2(NH₃)(H₂O) (16), which are characterized by mass spectrometry, ¹H NMR spectroscopy, and elemental analyses. The geometry around ruthenium in 16 is pseudooctahedral with the NH₃ and H₂O ligands mutually trans. The Ru-O and Ru-N bond distances are 2.118(4) and 2.142(6) ?, respectively. Oxidation reactions of the above ruthenium hydrazine complexes are also studied.

Full text of DOI:10.1021/ic000291c

Inorg. Chem. 2000, 39, 5255-5264
5255
Ruthenium(II) Ammine and Hydrazine Complexes with [N(Ph2PQ)2]- (Q ) S, Se) Ligands
Qian-Feng Zhang,†,‡ Hegen Zheng,†,‡ Wai-Yeung Wong,§ Wing-Tak Wong,| and
Wa-Hung Leung*,†
Departments of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay,
Kowloon, Hong Kong, People’s Republic of China, The Hong Kong Baptist University, Kowloon Tong,
Kowloon, Hong Kong, People’s Republic of China, and The University of Hong Kong, Pokfulam Road,
Hong Kong, People’s Republic of China, and Coordination Chemistry Institute and Department of
Chemistry, Nanjing University, Nanjing 210093, People’s Republic of China
ReceiVed March 15, 2000
Reactions of coordinatively unsaturated Ru[N(Ph2PQ)2]2(PPh3) (Q ) S (1), Se (2)) with pyridine (py), SO2, and
NH3 afford the corresponding 18e adducts Ru[N(Ph2PQ)2]2(PPh3)(L) (Q ) S, L ) NH3 (5); Q ) Se, L ) py (3),
SO2 (4), NH3 (6)). The molecular structures of complexes 2 and 6 are determined. The geometry around Ru in
2 is pseudo square pyramidal with PPh3 occupying the apical position, while that in 6 is pseudooctahedral with
PPh3 and NH3 mutually cis. The Ru-P distances in 2 and 6 are 2.2025(11) and 2.2778(11) Å, respectively. The
Ru-N bond length in 6 is 2.185(3) Å. Treatment of 1 or 2 with substituted hydrazines L or NH2OH yields the
respective adducts Ru[N(Ph2PQ)2]2(PPh3)(L) (Q ) S, L ) NH2NH2 (12), t-BuNHNH2 (14), 1-aminopiperidine
(C5H10NNH2) (15); Q ) Se, L ) PhCONHNH2 (7), PhNHNH2 (8), NH2OH (9), t-BuNHNH2 (10), C5H10NNH2
(11), NH2NH2 (13)), which are isolated as mixtures of their trans and cis isomers. The structures of cis-14 and
cis-15 are characterized by X-ray crystallography. In both molecular structures, the ruthenium adopts a
pseudooctahedral arrangement with PPh3 and hydrazine mutually cis. The Ru-N bond lengths in cis-14‚CH2Cl2
and cis-15 are 2.152(3) and 2.101(3) Å, respectively. The Ru-N-N bond angles in cis-14‚CH2Cl2 and cis-15 are
120.5(4) and 129.0(2)°, respectively. Treatment of 1 with hydrazine monohydrate leads to the isolation of yellow
5 and red trans-Ru[N(Ph2PS)2]2(NH3)(H2O) (16), which are characterized by mass spectrometry, 1H NMR
spectroscopy, and elemental analyses. The geometry around ruthenium in 16 is pseudooctahedral with the NH3
and H2O ligands mutually trans. The Ru-O and Ru-N bond distances are 2.118(4) and 2.142(6) Å, respectively.
Oxidation reactions of the above ruthenium hydrazine complexes are also studied.
Introduction
taining d6 metal centers such as Mo(0), W(0), Re(I), Ru(II),
and Os(II).4-7 Diazene, which is highly reactive in its free state,
can be stabilized by coordination to transition metals. Sellmann
and co-workers isolated binuclear Ru(II) diazene complexes with
polydentate thiolate ligands by air oxidation of the Ru(II)
hydrazine precursors. The solid-state structures of these bi-
Transition-metal diazene (NHdNH) and hydrazine complexes
are of current interest because these species are believed to be
possible intermediates in the biological reduction of nitrogen.1
The structural identification of the resting state of the FeMo
cofactor of nitrogenases as an [MoFe7S9] cluster core inspires
new speculation on the molecular mechanism of biological
nitrogen fixation.2 Recently, Coucouvanis and co-workers
demonstrated that an Fe/Mo/S cubane-like cluster is capable of
catalyzing the disproportionation of N2H4 to NH3, suggesting
that the Mo center in the FeMo cofactor may play a role in
nitrogen fixation, at least in the reduction of hydrazine.3 The
most extensively studied hydrazine complexes are those con-
(4) (a) Sellmann, D.; Sutter, J. In Transition Metal Sulfur Chemistry:
Biological and Industrial Significance; Stiefel, E. I., Matsumoto, K.,
Eds.; ACS Symposium Series 653; American Chemical Society:
Washington, DC, 1996; p 101 and references therein. (b) Nugent, W.
A.; Haymore, B. L. Coord. Chem. ReV. 1980, 31, 123. (c) Schrock,
R. R.; Glassman, T. E.; Vale, M. G. J. Am. Chem. Soc. 1991, 113,
725. (d) Sellmann, D.; Lechner, P.; Knoch, F.; Moll, M. J. Am. Chem.
Soc. 1992, 114, 922. (e) Heaton, B. T.; Jacob, C.; Page, P. Coord.
Chem. ReV. 1996, 154, 193.
(5) (a) Southern, J. S.; Hillhouse, G. L. J. Am. Chem. Soc. 1997, 119,
12406. (b) Cheng, T.-Y.; Perters, J. C.; Hillhouse, G. L. J. Am. Chem.
Soc. 1994, 116, 204. (c) Cheng, T.-Y.; Ponce, A.; Rheingold, A. L.;
Hillhouse, G. L. Angew. Chem., Int. Ed. Engl. 1994, 33, 657. (d) Smith,
M. R., III; Cheng, T.-Y.; Hillhouse, G. L. J. Am. Chem. Soc. 1993,
115, 8638.
(6) (a) Sellmann, D.; Kunstmann, H.; Knoch, F.; Moll, M. Inorg. Chem.
1988, 27, 4183. (b) Sellmann, D.; Soglowek, W.; Knoch, F.; Moll,
M. Angew. Chem., Int. Ed. Engl. 1989, 28, 1272. (c) Sellmann, D.;
Soglowek, W.; Knoch, F.; Ritter, G.; Dengler, J. Inorg. Chem. 1992,
31, 3711. (d) Sellmann, D.; Ka¨ppler, J.; Moll, M.; Knoch, F. Inorg.
Chem. 1993, 32, 960. (e) Sellmann, D.; Friedrich, H.; Knoch, F.; Moll,
M. Z. Naturforsch. 1994, 49B, 660. (f) Sellmann, D.; Gottschalk-
Gaudig, T.; Heinemann, F. W. Inorg. Chem. 1998, 37, 3982. (g)
Sellmann, D.; Engl, K.; Heinemann, F. W. Eur. J. Inorg. Chem. 2000,
423. (h) Sellmann, D.; Engl, K.; Heinemann, F. W.; Sieler, J. Eur. J.
Inorg. Chem. 2000, 1079.
* Corresponding author. Email: chleung@ust.hk.
† The Hong Kong University of Science and Technology;
‡
Nanjing University.
§ The Hong Kong Baptist University.
| The University of Hong Kong.
(1) (a) Chatt, J.; Richards, R. L. In The Chemistry and Biochemistry of
Nitrogen Fixation; Postgate, J. R., Ed.; Plenum: London, 1971. (b)
Zollinger, H. Diazo Chemistry II; VCH: Weinheim, Germany, 1995.
(c) Hidai, M.; Mizobe, Y. Chem. ReV. 1995, 95, 1115. (d) Sutton, D.
Chem. ReV. 1993, 93, 935. (e) Sellmann, D. Angew. Chem., Int. Ed.
Engl. 1993, 32, 64. (f) Kisch, H.; Holzmerier, P. AdV. Organomet.
Chem. 1992, 34, 67.
(2) (a) Chan, M. K.; Kim, J.; Rees, D. C. Science 1993, 260, 792. (b)
Kim, J.; Woo, D.; Rees, D. C. Biochemistry 1993, 32, 7104.
(3) (a) Demadis, K. D.; Coucouvanis, D. Inorg. Chem. 1995, 34, 3658.
(b) Demadis, K. D.; Campana, C. F.; Coucouvanis, D. J. Am. Chem.
Soc. 1995, 117, 7832.
10.1021/ic000291c CCC: $19.00 © 2000 American Chemical Society
Published on Web 10/26/2000

5256 Inorganic Chemistry, Vol. 39, No. 23, 2000
Zhang et al.
previously reported method.10 K[N(Ph2PQ)2] (Q ) S, Se) were
nuclear Ru diazene complexes reveal that the bridging diazene
ligand is stabilized by intramolecular S‚‚‚H-N hydrogen bonds.6
Mononuclear diazene complexes of W, Ru, and Os have also
been prepared by Pb(IV) oxidation of the respective hydrazine
precursors.5 To our knowledge, no Ru hydrazine complexes with
selenide ligands are known to date. To this end, we set out to
prepare Ru hydrazine complexes containing chelating sulfide
and selenide ligands and studied their oxidation reactions. Of
particular interest are Ru complexes with sterically bulky
iminobis(phosphinechalcogenide) ligands (R2PQ)2NH (R ) Ph,
i-Pr; Q ) S, Se). Metal complexes with the bidentate chelating
ligands [N(R2PQ)2]- (Q ) O, S, Se; R ) alkyl or phenyl) (e.g.,
structure I) are known to exhibit interesting stereochemistry.8
12
synthesized by deprotonation of HN(Ph2PQ)2 with potassium tert-
13
butoxide in methanol, and Ru(PPh3)3Cl2 was obtained from the
reaction RuCl3‚xH2O and PPh3 in MeOH. A 35% solution of NH2NH2
in water, hydrazine monohydrate N2H4‚H2O, t-BuNHNH2, PhNHNH2,
PhCONHNH2, NH2OH, and 1-aminopiperidine (C5H10NNH2) were
purchased from Aldrich. Other reagents were obtained from commercial
sources and used as received.
NMR spectra were recorded on a Bruker ALX 300 spectrometer
operating at 300 and 121.5 MHz for 1H and 31P, respectively. Chemical
shifts (δ, ppm) are reported with reference to SiMe4 (1H) and 85%
H3PO4 (31P). Infrared spectra were recorded on a Perkin-Elmer 16 PC
FT-IR spectrophotometer, and mass spectra were obtained on a Finnigan
TSQ 7000 spectrometer. Cyclic voltammetry was performed with a
Princeton Applied Research (PAR) model 273A potentiostat. The
working and reference electrodes were glassy carbon and Ag/AgNO3
(0.1 M in acetonitrile) electrodes, respectively. Potentials are reported
with reference to the ferrocenium-ferrocene (Cp2Fe+/0) couple. El-
emental analyses were performed by Medac Ltd., Surrey, U.K.
Preparation of Ru[N(Ph2PSe)2]2(PPh3), 2. A mixture of Ru(PPh3)3-
Cl2 (0.50 mg, 0.52 mmol) and K[N(Ph2PSe)2] (0.58 mg, 1.00 mmol)
in tetrahydrofuran (THF) (40 mL) was stirred overnight at room
temperature, during which there was a color change from brown to
dark green. The solvent was pumped off, and the residue was washed
with Et2O. Recrystallization from CH2Cl2/Et2O afforded dark-green
block-shaped crystals of 2, which were suitable for X-ray diffraction
study. Yield: 0.52 g, 69%. 1H NMR (CDCl3): δ 7.33-7.94 (m, phenyl
protons). 31P{1H} NMR (CDCl3): δ 34.53 (s, N(Ph2PSe)2), 23.19 (s,
PPh3). IR (KBr; cm-1): 1172(s) and 800(s) [ν(P2N)], 532(vs) [ν(Pd
Se)]. MS (FAB): m/z 1448 (M+), 1187 (M+ - PPh3). E1/2 (CH2Cl2;
V): -0.17 [Ru(III/II)]. Anal. Calcd for C66H55N2P5Se4Ru: C, 54.75;
H, 3.83; N, 1.94. Found: C, 55.23; H, 4.14; N, 1.92.
Preparation of trans-Ru[N(Ph2PSe)2]2(PPh3)(py) (py ) Pyridine),
trans-3. Excess py was added to a well-stirred solution of 2 (80 mg,
0.055 mmol) in THF (15 mL). The green solution immediately became
yellow, and a large amount of orange solid precipitated. After 15 min
of stirring, the solvent was removed and the solid product was isolated.
Recrystallization from CH2Cl2/Et2O afforded orange needles of 3.
Yield: 79 mg, 94%. 1H NMR (CDCl3): δ 7.30-7.55 (m, 45H, phenyl
protons), 7.66-7.76 (br, 5H, py). 31P{1H} NMR (CDCl3): δ 22.45 (d,
2JP-P ) 3.4 Hz, N(Ph2PSe)2), 45.19 (m, PPh3). IR (KBr; cm-1): 1480-
(s) [ν(CdN)], 1174(s) and 807(s) [ν(P2N)], 534(vs) [ν(PdSe)]. MS
(FAB): m/z 1448 (M+ - py), 1187 (M+ - py - PPh3 + 1). E1/2 (CH2-
Cl2; V): -0.21 [Ru(III/II)]. Anal. Calcd for C71H60N3P5Se4Ru: C, 55.84;
H, 3.96; N, 2.75. Found: C, 55.80; H, 4.00; N, 2.64.
The geometry of the M[N(PR2E)2] metallacycle is very flexible
and can be tuned by judicious choice of the peripheral alkyl
groups and the chalcogenides at two ends of the diphosphazene
fragment.8 Due to strong metal-chalcogenide interactions in
the six-membered M[N(R2PQ)2] ring, it is possible to generate
and stabilize highly reactive unsaturated molecular fragments
M[N(PR2E)2]2, which can be used for the activation of small
molecules. Woollins and co-workers first isolated Ru cluster
compounds with [N(R2PQ)2]- by reactions of (R2PQ)2NH with
Ru3(CO)12.9 Recently, we reported the isolation of 16e Ru[N(R2-
PS)2]2(PPh3) (R ) Ph, i-Pr), which show weak Ru-C-H
agostic interactions in the solid state. These coordinatively
unsaturated Ru/S complexes form adducts readily with pyridine
and are capable of activating H2 and SO2.10 Five-coordinate Ru-
[N(R2PS)2]2(dCHPh) was found to be an active catalyst for
the ring-opening polymerization of norbornene.11 In this paper,
we describe the syntheses of Ru hydrazine complexes with
[N(Ph2PQ)2]- (Q ) S, or Se) and the oxidation reactions of
these complexes.
Preparation of cis- and trans-Ru[N(Ph2PSe)2]2(PPh3)(SO2), cis-
and trans-4. Through a solution of 2 (90 mg, 0.062 mmol) in THF
(20 mL) was bubbled SO2(g) for 30 s, during which the color of the
solution changed from green to orange. The resulting mixture was stirred
for 1 h at room temperature and then evaporated to dryness, after which
the residue was washed with hexane. Recrystallization from CH2Cl2/
hexane afforded red rhombohedral crystals. Yield: 64 mg (68%). The
Experimental Section
General Considerations. Solvents were purified by standard
procedures and distilled prior to use. All manipulations, unless otherwise
stated, were carried out under nitrogen using standard Schlenk
techniques. Ru[N(Ph2PS)2]2(PPh3) (1) was prepared according to our
1
product was found to consist of cis and trans forms in solution. H
(7) (a) Hough, J. J.; Singleton, E. J. Chem. Soc., Chem. Commun. 1972,
371. (b) Ashworth, T. V.; Nolte, M. J.; Singleton, E. J. Chem. Soc.,
Dalton Trans. 1978, 1040. (c) Blum, L.; Williams, I. D.; Schrock, R.
R. J. Am. Chem. Soc. 1984, 106, 8316. (d) Collman, J. P.; Hutchison,
J. E.; Lopez, M. A.; Guilard, R.; Reed, R. A. J. Am. Chem. Soc. 1991,
113, 2794. (e) Kawano, M.; Hoshino, C.; Matsumoto, K. Inorg. Chem.
1992, 31, 5158. (f) Coia, G. M.; Devenney, M.; White, P. S.; Meyer,
T. J. Inorg. Chem. 1997, 36, 2341. (g) Furuhashi, T.; Kawano, M.;
Koide, Y.; Somazawa, R.; Matsumoto, K. Inorg. Chem. 1999, 38, 109.
(h) Sun, X.-R.; Huang, J.-S.; Cheung, K.-K.; Che, C.-M. Inorg. Chem.
2000, 39, 820.
(8) (a) Ly, T. Q.; Woollins, J. D. Coord. Chem. ReV. 1998, 176, 451. (b)
Cupertino, D.; Keyte, R.; Slawin, A. M. Z.; Williams, D. J.; Woollins,
J. D. Inorg. Chem. 1996, 35, 2695. (c) Bhattacharyya, P.; Slawin, A.
M. Z.; Williams, D. J.; Woollins, J. D. J. Chem. Soc., Dalton Trans.
1995, 3189.
NMR (CDCl3): δ 6.53-7.76 (m, phenyl protons). 31P{1H} NMR
2
(CDCl3): trans-4 δ 25.80 (d, JP-P ) 12 Hz, N(Ph2Se)2), 55.38 (m,
PPh3); cis-4 δ 19.42, 23.11, 45.13, 47.26, 55.98 (all multiplets). IR
(KBr; cm-1): 1214(m) and 810(s) [ν(P2N)], 531(vs) [ν(PdSe)], 1017-
(vs), 996(vs) [ν(SdO)]. MS (FAB): m/z 1448 (M+ - SO2). Anal. Calcd
for C66H55N3O2P5SSe4Ru: C, 52.43; H, 3.67; N, 1.85. Found: C, 52.38;
H, 3.92; N, 2.02.
Preparations of cis- and trans-Ru[N(Ph2PQ)2]2(PPh3)(NH3) (Q
) S )5), Se (6)). These complexes were prepared similarly to 4 by
treating 1 and 2 with NH3(g). The products were isolated as yellow
(for 5) and red (for 6) crystals. Both were found to exist as their cis
and trans forms in solution.
(9) Alexandra, M. Z. S.; Smith, M. B.; Woollins, J. D. J. Chem. Soc.,
Dalton Trans. 1997, 1877.
(10) Leung, W.-H.; Zheng, H.; Chim, J. L. C.; Chan, J.; Wong, W.-T.;
Williams, I. D. J. Chem. Soc., Dalton Trans. 2000, 423.
(11) Leung, W.-H.; Lau, K.-K.; Zhang, Q.-F.; Wong, W.-T.; Tang, B.-Z.
Organometallics 2000, 19, 2084.
(12) (a) Wang, F. T.; Najdzionek, J.; Leneker, K. L.; Wasserman, H.;
Braitsch, D. M. Inorg. Synth. Met-Org. Chem. 1978, 8, 120. (b)
Bhattacharyya, P.; Novosad, J.; Phillips, J.; Slawin, A. M. Z.; Williams,
D. J.; Woollins, J. D. J. Chem. Soc., Dalton Trans. 1995, 1607.
(13) Stephenson, T. A.; Wilkinson, G. J. Inorg. Nucl. Chem. 1966, 28,
945.

Ruthenium(II) Ammine and Hydrazine Complexes
Inorganic Chemistry, Vol. 39, No. 23, 2000 5257
Yield of 5: 35 mg, 35%. 1H NMR (CDCl3): δ 1.00 (br s, 3H, NH3),
2.6 (br s, 3H, NH3), 7.07-8.13 (m, 110H, phenyl protons). 31P{1H}
NMR (CDCl3): trans-5 δ 37.89 (d, 2JP-P ) 3.6 Hz, N(Ph2PS)2), 46.53
(m, PPh3); cis-5, δ 36.14, 38.58, 38.92, 40.56, 50.28 (all multiplets).
IR (KBr; cm-1): 3335(m) [ν(N-H)], 1178(s) and 800(s) [ν(P2N)], 565-
(vs) [ν(PdS)]. MS (FAB): m/z 1260 (M+ - NH3). E1/2 (CH2Cl2; V):
-0.31 [Ru(III/II)]. Anal. Calcd for C66H58N3P5S4Ru: C, 61.4; H, 4.5;
N, 3.1. Found: C, 62.1; H, 4.5; N, 3.3.
Yield of 6: 59 mg, 62%. 1H NMR (CDCl3): δ 0.99 (br s, 3H, NH3),
2.71 (br s, 3H, NH3), 6.81-7.83 (m, 110H, phenyl protons). 31P{1H}
NMR (CDCl3): trans-6 δ 21.12 (d, 2JP-P ) 3.5 Hz, N(Ph2PSe)2), 48.83
(m, PPh3); cis-6 δ 18.51, 22.04, 22.73, 27.30, 51.64 (all multiplets).
IR (KBr; cm-1): 3336(m) [ν(N-H)], 1201(s) and 804(s) [ν(P2N)], 532-
(vs) [ν(PdSe)]. MS (FAB): m/z 1448 (M+ - NH3), 1187 (M+ - NH3
- PPh3). E1/2 (CH2Cl2; V): -0.21 [Ru(III/II)]. Anal. Calcd for
C66H58N3P5Se4Ru: C, 54.11; H, 3.99; N, 2.87. Found: C, 54.38; H,
4.17; N, 2.92.
(FAB): m/z 1447 (M+ - C5H10NNH2). E1/2 (CH2Cl2; V): -0.23 [Ru-
(III/II)]. Anal. Calcd for C71H67N4P5Se4Ru: C, 55.08; H, 4.36; N, 3.62.
Found: C, 54.70; H, 4.39; N, 3.42.
Preparations of cis- and trans-Ru[N(Ph2PQ)2]2(PPh3)(NH2NH2)
(Q ) S (12), Se (13)). These complexes were prepared similarly to 7
by using excess 35% NH2NH2 in H2O. Both were found to exist as
1
their cis and trans forms in solutions. Yield of 12: 20 mg, 21%. H
NMR (CDCl3): δ 5.29 (br s, NH2), 5.33 (br s, RuNH2), 7.00-8.42
(m, phenyl protons). 31P{1H} NMR (CDCl3): trans-12 δ 37.87 (d, 2JP-P
) 3.4 Hz, N(Ph2PS)2), 46.51 (m, PPh3); cis-12 δ 38.37, 38.77, 40.44,
46.50, 50.17 (all multiplets). IR (KBr; cm-1): 3307(w), 3286(w) [ν-
(N-H)], 1258(s), 1154(m) and 802(s) [ν(P2N)], 564(vs) [ν(PdS)]. MS
(FAB): m/z 998 (M+ - N2H4 - PPh3 + 1). Anal. Calcd for
C66H59N4P5S4Ru: C, 61.43; H, 4.53; N, 4.34. Found: C, 60.98; H,
4.61; N, 4.36.
1
Yield of 13: 74 mg, 72%. H NMR (CDCl3): δ 0.86 (br s, NH2),
3.75 (br s, RuNH2), 6.51-7.61 (m, phenyl protons). 31P{1H} NMR
(CDCl3): trans-13 δ 42.07 (d, 2JP-P ) 44 Hz, N(Ph2PSe)2), 89.51 (m,
PPh3); cis-13 δ 18.56, 22.05, 22.76, 27.35, 48.45 (all multiplets). IR
(KBr; cm-1): 3358(m) [ν(N-H)], 1138(s) and 780(s) [ν(P2N)], 540-
Preparation of cis- and trans-Ru[N(Ph2PSe)2]2(PPh3)(PhCONH-
NH2), cis- and trans-7. To a solution of 2 (100 mg, 0.069 mmol) in
THF (25 mL) was added PhCONHNH2 (10 mg, 0.070 mmol) in THF
(5 mL), and the mixture was stirred at room temperature for 3 h, during
which there was a color change from green to dark orange. The solvent
was pumped off, and the residue was washed with hexane. Recrystal-
lization from CH2Cl2/hexane afforded orange crystals. Yield: 58 mg,
53%. The product was found to consist of cis and trans forms of 7 in
solution. 1H NMR (CDCl3): δ 4.87 (m, RuNH2), 6.72-7.65 (m, phenyl
protons), 7.90 (t, NH). 31P{1H} NMR (CDCl3): trans-7 δ 22.67 (d,
2JP-P ) 6.4 Hz, N(Ph2PSe)2), 62.66 (m, PPh3); cis-7 δ 20.76, 21.81,
23.65, 25.13, 20.76 (all multiplets). IR (KBr; cm-1): 3227(w), 3211-
(w) [ν(N-H)], 1632(s) [ν(CdO)], 1206(vs) and 798(s) [ν(P2N)], 536-
(vs) [ν(PdSe)]. E1/2 (CH2Cl2; V): -0.19 [Ru(III/II)]. Anal. Calcd for
C73H63N4OP5Se4Ru: C, 55.35; H, 4.01; N, 3.54. Found: C, 55.25; H,
4.15; N, 3.82.
(vs) [ν(PdSe)]. MS (FAB): m/z 1449 (M+ - N2H4), 1186 (M+
-
N2H4 - PPh3). Anal. Calcd for C66H59N4P5Se4Ru: C, 53.56; H, 4.02;
N, 3.78. Found: C, 53.71; H, 4.03; N, 3.45.
Preparations of cis- and trans-Ru[N(Ph2PS)2]2(PPh3)(L) (L )
t-BuNHNH2 (14), C5H10NNH2 (15)). The procedure for the synthesis
of 12 was followed using 1 as the starting material to prepare 14 and
15. Both complexes were found to exist as their cis and trans forms in
solution.
Yield of 14: 74%. 1H NMR (CDCl3): δ 1.42 (s, 9H, t-Bu), 2.39 (br
s, NH), 4.82 (br s, RuNH2), 6.86-7.76 (m, 55H, phenyl protons). 31P-
{1H} NMR (CDCl3): trans-14 δ 35.27 (d, 2JP-P ) 6.2 Hz, N(Ph2PS)2),
78.96 (br m, PPh3); cis-14 δ 36.21, 37.67, 38.65, 41.15, 50.75, (all
multiplets). IR (KBr; cm-1): 3208(w), 3201(w) [ν(N-H)], 1172(s) and
802(s) [ν(P2N)], 564(vs) [ν(PdS)]. MS (FAB): m/z 1349 (M+), 1260
(M+ - t-BuNHNH2), 998 (M+ - t-BuNHNH2 - PPh3 + 1). E1/2 (CH2-
Cl2; V): -0.14 [Ru(III/II)]. Anal. Calcd for C70H66N4P5S4Ru: C, 60.61;
H, 4.94; N, 4.16. Found: C, 59.68; H, 5.08; N, 4.10.
Preparations of cis- and trans-Ru[N(Ph2PSe)2]2(PPh3)(L) (L )
PhNHNH2 (8), NH2OH (9), t-BuNHNH2 (10), C5H10NNH2 (11)).
These complexes were prepared similarly to 7 by using PhNHNH2,
NH2OH, t-BuNHNH2, and C5H10NNH2, respectively, instead of Ph-
CONHNH2. The products were found to exist as their cis and trans
forms in solutions.
Yield of 8: 50 mg, 46%. 1H NMR (CDCl3): δ 6.81-7.83 (m, phenyl
protons); NH signals not assigned. 31P{1H} NMR (CDCl3): trans-8 δ
21.10 (d, 2JP-P ) 6.8 Hz, N(Ph2PSe)2), 48.62 (m, PPh3); cis-8 δ 18.39,
22.10, 23.51, 27.34, 52.01 (all multiplets). IR (KBr; cm-1): 3347(w),
3252(w) [ν(N-H)], 1206(s) and 794(s) [ν(P2N)], 532(vs) [ν(PdSe)].
E1/2 (CH2Cl2; V): -0.20 [Ru(III/II)]. Anal. Calcd for C72H63N4P5Se4-
Ru‚H2O: C, 54.90; H, 4.13; N, 3.56. Found: C, 54.56; H, 4.41; N,
3.45.
Yield of 15: 82 mg, 68%. 1H NMR (CDCl3): δ 1.26 (d, 2Hγ, C5H10),
1.63 (d, 4Hâ, C5H10), 2.60 (m, 4HR, C5H10), 6.76 (br s, 2H, NH2), 7.00-
7.77 (m, 55H, phenyl protons). 31P{1H} NMR (CDCl3): trans-15 δ
36.23 (d, 2JP-P ) 3.6 Hz, N(Ph2PS)2), 50.24 (m, PPh3); cis-15 δ 37.63,
37.88, 38.23, 39.96, 46.53, (all multiplets). IR (KBr; cm-1): 3294(w)
[ν(N-H)], 1199(s), 1170(m) and 796(s) [ν(P2N)], 564(vs) [ν(PdS)].
MS (FAB): m/z 1359 (M+), 1260 (M+ - C5H10NNH2), 999 (M+
-
C5H10NNH2 - PPh3 + 1). E1/2 (CH2Cl2; V): -0.16 [Ru(III/II)]. Anal.
Calcd for C71H67N4P5S4Ru: C, 58.32; H, 4.58; N, 3.66. Found: C,
58.65; H, 4.59; N, 3.32.
Yield of 9: 55 mg, 54%. 1H NMR (CDCl3): δ 2.81 (br s, RuNH2),
Reaction of 1 with Hydrazine Monohydrate. To a solution of 1
(0.10 g, 0.079 mmol) in THF (15 mL) was added hydrazine monohy-
drate (ca. 0.03 mL). The resulting clear solution was stirred at room
temperature for 30 min and then evaporated to dryness. The resulting
red residue was washed with Et2O and dissolved in 8 mL of CH2Cl2,
and the mixture was filtered. The red filtrate, layered with Et2O, was
left to stand at room temperature for 3 days. The red blocks (49 mg)
and yellow powder (43 mg) that formed were separated manually and
were characterized as trans-Ru[N(Ph2PS)2]2(NH3)(H2O) (16) and cis-
Ru[N(Ph2PS)2]2(PPh3)(NH3) (5), respectively. Characterization data for
16 are as follows. 1H NMR (CDCl3): δ 1.55 (br s, 2H, H2O), 2.60 (br
s, 3H, NH3), 6.86-7.88 (m, 40H, phenyl protons). 31P{1H} NMR
6.83-7.75 (m, phenyl protons), 8.27 (br s, OH). 31P{1H} NMR
2
(CDCl3): trans-9 δ 22.67 (d, JP-P ) 6.4 Hz, N(Ph2PSe)2), 64.23 (m,
PPh3); cis-9 δ 21.06, 21.81, 23.65, 24.84, 25.13 (all multiplets). IR
(Nujol, cm-1): 3450(br) [ν(O-H)], 3269(w) [ν(N-H)], 1230(s), 1176-
(m) and 797(s) [ν(P2N)], 532(vs) [ν(PdSe)]. E1/2 (CH2Cl2; V): -0.19
[Ru(III/II)]. Anal. Calcd for C66H58N3OP5Se4Ru: C, 53.53; H, 3.95;
N, 2.84. Found: C, 54.59; H, 4.33; N, 2.73.
Yield of 10: 60 mg, 47%. 1H NMR (CDCl3): δ 1.40 (s, 9H, t-Bu),
2.35 (br s, NH), 4.81 (br s, RuNH2), 6.87-7.71 (m, 55H, phenyl
2
protons). 31P{1H} NMR (CDCl3): trans-10 δ 21.16 (d, JP-P ) 3.3
Hz, N(Ph2PSe)2), 48.62 (m, PPh3); cis-10 δ 18.72, 21.91, 22.65, 27.85,
50.13 (all multiplets). IR (KBr; cm-1): 3348(w) [ν(N-H)], 1202(s),
1152(m) and 784(s) [ν(P2N)], 532(vs) [ν(PdSe)]. MS (FAB): m/z 1449
(M+ - t-BuNHNH2), 1186 (M+ - t-BuNHNH2 - PPh3). E1/2 (CH2-
Cl2; V): -0.26 [Ru(III/II)]. Anal. Calcd for C70H67N4P5Se4Ru: C, 54.73;
H, 4.40; N, 3.65. Found: C, 55.12; H, 4.32; N, 3.55.
Yield of 11: 69 mg, 54%. 1H NMR (CDCl3): δ 1.27 (d, 2Hγ, C5H10),
1.67 (d, 4Hâ, C5H10), 2.71 (br s, R-4H, C5H10), 6.83 (br s, 2H, NH2),
7.04-7.84 (m, 55H, phenyl protons). 31P{1H} NMR (CDCl3): trans-
11 δ 21.11 (d, 2JP-P ) 3.4 Hz, N(Ph2PSe)2), 48.83 (m, PPh3); cis-11 δ
18.48, 21.96, 22.64, 27.25, 50.81 (all multiplets). IR (KBr; cm-1): 3352-
(w) [ν(N-H)], 1202(s) and 795(s) [ν(P2N)], 532(vs) [ν(PdSe)]. MS
2
(CDCl3): δ 37.89 (d, JP-P ) 2.5 Hz, N(Ph2PS)2). IR (KBr; cm-1):
3422 (br m) [ν(H2O)], 3284(m) [ν(N-H)], 1238(s), 1140(s) and 807-
(s) [ν(P2N)], 562(vs) [ν(PdS)]. MS (FAB): m/z 1032 (M+), 1014 (M+
- H2O - 1), 998 (M+ - H2O - PPh3 - NH3 + 1). Anal. Calcd for
C48H45N3OP4S4Ru: C, 55.80; H, 4.39; N, 4.07. Found: C, 55.82; H,
4.16; N, 4.16.
Oxidation of 13 with Pb(OAc)4. To a stirred solution of 13 (80
mg, 0.054 mmol) in CH2Cl2 (5 mL) at -78 °C was slowly added Pb-
(OAc)4 (25 mg, 0.060 mmol) in CH2Cl2 (5 mL). There was a color
change from orange to green upon warming the mixture to ambient
temperature. The resulting solution was filtered, and the filtrate was

5258 Inorganic Chemistry, Vol. 39, No. 23, 2000
Zhang et al.
Table 1. Crystal Data and Structure Refinement Details for Ru[N(Ph2PSe)2]2(PPh3) (2), cis-Ru[N(Ph2PSe)2]2(PPh3)(NH3)‚CH2Cl2
(cis-6‚CH2Cl2), cis-Ru[N(Ph2PS)2]2(PPh3)(t-BuNHNH2)‚CH2Cl2 (cis-14‚CH2Cl2), cis-Ru[N(Ph2PS)2]2(PPh3)(C5H10NNH2) (cis-15), and
trans-Ru[N(Ph2PS)2]2(H2O)(NH3) (16)
2
cis-6‚CH2Cl2
cis-14‚CH2Cl2
cis-15
16
empirical formula
fw
crystal system
space group
a, Å
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
C66H55N2P5Se4Ru
1447.88
monoclinic
P21/c (No. 14)
10.4401(5)
26.6189(13)
25.1173(12)
C67H60N3Cl2P5Se4Ru
1549.84
triclinic
C71H68N4Cl2P5S4Ru
1432.35
triclinic
C71H67N4P5S4Ru
1360.45
monoclinic
P21/n (No. 14)
13.316(3)
20.094(4)
25.977(5)
C48H45N3OP4S4Ru
1033.11
triclinic
P1h (No. 2)
10.7575(8)
14.1661(8)
18.4217(9)
69.262(9)
86.401(9)
73.812(9)
2519.3(4)
2
P1h (No. 2)
13.0385(6)
14.1278(6)
19.5468(8)
90.4100(10)
102.1260(10)
109.5790(10)
3305.0(2)
2
P1h (No. 2)
13.3573(7)
14.5662(8)
19.9542(11)
75.0820(10)
89.6690(10)
62.8650(10)
3310.4(3)
2
98.4580(10)
100.73(3)
6904.3(6)
4
1.393
6829(2)
4
1.323
23
Z
F
calcd, g cm-3
1.557
23
1.437
23
1.362
23
temp, °C
23
F(000)
2880
24.89
15 388/0/703
0.903
1544
26.84
14 269/0/740
1.009
1478
6.11
14 281/0/785
0.944
2816
5.13
15 237/0/767
1.145
0.0504
0.1209a
1060
6.41
6343/0/550
1.35
µ(Mo KR), cm-1
no. of data/restraints/params
goodness-of-fit on F2
R1
0.0353
0.0410
0.0557
0.065
wR2 or Rw
0.1251a
0.1022a
0.1815a
0.063b
a wR2. b Rw.
Table 2. Selected Bond Lengths (Å) and Angles (deg) for
Ru[N(Ph2PSe)2]2(PPh3) (2)
concentrated to ca. 5 mL. Addition of diethyl ether led to the formation
of a paramagnetic black powder. IR (KBr; cm-1): 1205(m), 1151(s)
and 796(s) [ν(P2N)], 533(vs) [ν(PdSe)].
Bond Lengths
Ru(1)-Se(1)
Ru(1)-Se(3)
Ru(1)-P(5)
Se(2)-P(2)
Se(4)-P(4)
2.5269(5)
2.4828(5)
2.2025(11)
2.1835(11)
2.1946(12)
Ru(1)-Se(2)
Ru(1)-Se(4)
Se(1)-P(1)
Se(3)-P(3)
2.5410(5)
2.4561(5)
2.1809(11)
2.1837(11)
Air Oxidation of 12. A CH2Cl2 (10 mL) solution of 12 (0.10 g,
0.077 mmol) was stirred under an atmosphere of dry air overnight at
room temperature, during which the solution gradually turned green.
The greenish-yellow mixture was filtered, and the filtrate was layered
with hexane. Yellow crystals analyzed as Ru[N(Ph2PS)2]2(PPh3)(N2H2)
(18) were obtained in low yield (15 mg, 17%), along with a large
amount of uncharacterized black precipitate. Characterization data for
18 are as follows: 1H NMR (CDCl3): δ 7.05-8.10 (m, phenyl protons);
NH signals not detected. 31P{1H} NMR (CDCl3): δ 36.65, 36.73, 40.56,
41.94, 50.17 (all multiplets). IR (KBr; cm-1): 3341(w) and 3330(w)
[ν(N-H)], 1572(m) [ν(NdN)], 1258(s) and 801(s) [ν(P2N)], 564(vs)
[ν(PdS)]. MS (FAB): m/z 1260 (M+ - N2H2), 998 (M+ - N2H2 -
PPh3 + 1). Anal. Calcd for C66H57N4P5S4Ru‚CH2Cl2: C, 58.56; H, 4.43;
N, 4.02. Found: C, 59.14; H, 4.44; N, 3.86.
Bond Angles
Se(1)-Ru(1)-Se(2) 87.715(17) Se(3)-Ru(1)-Se(4) 99.984(18)
Se(1)-Ru(1)-Se(4) 160.13(2) Se(2)-Ru(1)-Se(3) 160.946(19)
Se(1)-Ru(1)-Se(3) 84.885(17) Se(2)-Ru(1)-Se(4) 81.546(17)
P(5)-Ru(1)-Se(1) 92.05(3) P(5)-Ru(1)-Se(2) 94.28(3)
P(5)-Ru(1)-Se(3) 103.50(3) P(5)-Ru(1)-Se(4) 105.32(3)
P(1)-Se(1)-Ru(1) 95.48(3) P(2)-Se(2)-Ru(1) 97.77(3)
P(3)-Se(3)-Ru(1) 112.72(3) P(4)-Se(4)-Ru(1) 112.19(3)
group in the tert-butyl moiety were refined isotropically. Hydrogen
atoms in the phenyl and other organic moieties were treated as idealized
contributions except for the hydrogen atoms of H2O and NH3 in
complex 16, which were located by a difference Fourier synthesis based
on low-angle data (θ < 15°) and refined. Crystallographic data and
experimental details are listed in Table 1. Selected bond distances and
angles for 2, cis-6‚CH2Cl2, cis-14‚CH2Cl2, cis-15, and 16 are given in
Tables 2-6, respectively.
X-ray Crystallographic Studies. Single crystals of 2 (black-green),
cis-6‚CH2Cl2 (orange-red), cis-14‚CH2Cl2 (orange), cis-15 (orange), and
16 (red) were obtained by slow diffusion of diethyl ether into CH2Cl2
solutions of the complexes. Diffraction data for 2, cis-6‚CH2Cl2, cis-
14‚CH2Cl2, and cis-15 were collected at room temperature on a Bruker
SMART CCD area-detector diffractometer using graphite-monochro-
mated Mo KR radiation (λ ) 0.710 73 Å). Cell parameters and
orientation matrices for these structures were obtained from the least-
squares refinements of reflections measured in three different sets of
15 frames each. The collected frames were processed with the software
SAINT,14a and an absorption correction was applied (SADABS14b) to
the collected reflections. Diffraction data for 16 were collected on a
Rigaku ACF7R diffractometer with the use of graphite-monochromated
Mo KR radiation (λ ) 0.710 73 Å). The structures were solved by
direct methods in conjunction with standard difference Fourier tech-
niques and subsequently refined by full-matrix least-squares analyses.
All calculations were done by the program packages SHELXTL V5.015
(for 2, cis-6‚CH2Cl2, cis-14, and cis-15) and TEXSAN16 (for 16). Non-
hydrogen atoms for 2, cis-6‚CH2Cl2, cis-14, and 16 were refined
anisotropically. For cis-14‚CH2Cl2, three carbon atoms of one methyl
Results and Discussion
Synthesis and Characterization of Ru[N(Ph2PSe)2]2(PPh3).
Treatment of Ru(PPh3)3Cl2 with K[N(Ph2PSe)2] in THF gave
Ru[N(Ph2PSe)2]2(PPh3) (2) as the sole isolable product. The KBr
IR spectrum of 2 shows the ν(P2N) bands at 1172(s) and 800-
(s) cm-1 and the ν(PdSe) band at 532(vs) cm-1, reflecting the
increase in P-N bond order and decrease in PdSe double-bond
character for the [N(Ph2PSe)2]- ligand compared to its proto-
nated form HN(Ph2PSe)2 [ν(P2N) at 937, 926, and 918 cm-1
;
ν(PdSe) at 595 and 546 cm-1].12b The 31P{1H} NMR spectrum
of 2 in CDCl3 shows an intense singlet at δ 34.53 and a weak
singlet at δ 23.19, assignable to [N(Ph2PSe)2]- and PPh3,
respectively. The 31P resonant signal for [N(Ph2PSe)2]- in 2 (δ
34.5) is less downfield than that for Ru[N(PPh2S)2]2(PPh3) (1)
(δ 37.8). A similar trend has also been found for the related
indium(III) (δ 33.2 for In[N(Ph2PS)2]3 versus δ 28.5 for In-
[N(Ph2PSe)2]3)17 and yttrium(III) (δ 47.8 for Cp2Y[N(Ph2PS)2]
(14) (a) SAINT Reference Manual; Siemens Energy and Automation Co.:
Madison, WI, 1994-1996. (b) Sheldrick, G. M. SADABS: Empirical
Absorption Correction Program; University of Go¨ttingen: Go¨ttingen,
Germany, 1997.
(15) Sheldrick, G. M. SHELXTL-Plus V5.1 Software Reference Manual;
Bruker AXS Inc.: Madison, WI, 1997.
(16) TEXSAN: Crystal Structure Package; Molecular Structure Corp.:
Houston, TX, 1985 and 1992.

Ruthenium(II) Ammine and Hydrazine Complexes
Inorganic Chemistry, Vol. 39, No. 23, 2000 5259
Table 3. Selected Bond Lengths (Å) and Angles (deg) for
cis-Ru[N(Ph2PSe)2]2(PPh3)(NH3)‚CH2Cl2 (cis-6·CH2Cl2)
Table 6. Selected Bond Lengths (Å) and Angles (deg) for
trans-Ru[N(Ph2PS)2]2(H2O)(NH3) (16)
Bond Lengths
BondLengths
Ru(1)-Se(1)
Ru(1)-Se(3)
Ru(1)-P(5)
Se(1)-P(1)
Se(3)-P(3)
2.5285(5)
2.6017(5)
2.2778(11)
2.1784(11)
2.1620(11)
Ru(1)-Se(2)
Ru(1)-Se(4)
Ru(1)-N(3)
Se(2)-P(2)
Se(4)-P(4)
2.5225(5)
2.5389(5)
2.185(3)
2.1869(11)
2.1737(11)
Ru(1)-S(1)
Ru(1)-S(3)
Ru(1)-O(1)
S(1)-P(1)
S(3)-P(3)
2.400(2)
2.430(2)
2.118(4)
2.009(3)
2.001(2)
Ru(1)-S(2)
Ru(1)-S(4)
Ru(1)-N(3)
S(2)-P(2)
S(4)-P(4)
2.402(2)
2.411(2)
2.142(6)
1.981(3)
2.017(2)
Bond Angles
Bond Angles
Se(1)-Ru(1)-Se(2) 99.768(17) Se(3)-Ru(1)-Se(4) 94.861(17)
Se(1)-Ru(1)-Se(4) 173.756(18) Se(2)-Ru(1)-Se(3) 88.997(17)
Se(1)-Ru(1)-Se(3) 88.400(17) Se(2)-Ru(1)-Se(4) 85.635(17)
S(1)-Ru(1)-S(2)
S(1)-Ru(1)-S(4)
S(1)-Ru(1)-S(3)
O(2)-Ru(1)-S(1)
O(2)-Ru(1)-S(3)
N(3)-Ru(1)-S(1)
N(3)-Ru(1)-S(3)
P(1)-S(1)-Ru(1)
P(3)-S(3)-Ru(1)
100.42(7) S(3)-Ru(1)-S(4)
170.75(7) S(2)-Ru(1)-S(3)
78.93(6) S(2)-Ru(1)-S(4)
101.43(6)
172.18(7)
80.48(7)
85.3(1)
95.3(1)
93.8(2)
85.3(2)
110.9(1)
109.43(9)
P(5)-Ru(1)-Se(1)
86.71(3)
P(5)-Ru(1)-Se(2)
P(5)-Ru(1)-Se(4)
N(3)-Ru(1)-Se(2) 172.10(9)
N(3)-Ru(1)-Se(4) 94.19(8)
P(1)-Se(1)-Ru(1) 111.09(3)
P(3)-Se(3)-Ru(1) 109.15(3)
92.87(3)
89.92(3)
93.9(1)
87.0(1)
85.4(2)
93.9(2)
O(2)-Ru(1)-S(2)
O(2)-Ru(1)-S(4)
N(3)-Ru(1)-S(2)
N(3)-Ru(1)-S(4)
P(5)-Ru(1)-Se(3) 174.99(3)
N(3)-Ru(1)-Se(1) 80.89(8)
N(3)-Ru(1)-Se(3) 83.15(9)
95.02(9)
P(2)-Se(2)-Ru(1) 107.48(3)
P(4)-Se(4)-Ru(1) 106.95(3)
N(3)-Ru(1)-P(5)
111.53(9) P(2)-S(2)-Ru(1)
109.11(9) P(4)-S(4)-Ru(1)
N(3)-Ru(1)-O(2) 178.8(2)
Table 4. Selected Bond Lengths (Å) and Angles (deg) for
cis-Ru[N(Ph2PS)2]2(PPh3)(t-BuNHNH2)‚CH2Cl2 (cis-14‚CH2Cl2)
Bond Lengths
Ru(1)-S(1)
Ru(1)-S(3)
Ru(1)-P(5)
N(3)-N(4)
S(2)-P(2)
S(4)-P(4)
2.4205(10)
2.4276(11)
2.2845(10)
1.451(8)
Ru(1)-S(2)
Ru(1)-S(4)
Ru(1)-N(3)
S(1)-P(1)
S(3)-P(3)
2.4051(10)
2.5159(10)
2.152(3)
2.0173(14)
2.0115(14)
2.0110(14)
1.9917(14)
Bond Angles
S(1)-Ru(1)-S(2)
S(1)-Ru(1)-S(4)
S(1)-Ru(1)-S(3)
P(5)-Ru(1)-S(1)
P(5)-Ru(1)-S(3)
95.41(4)
89.62(4)
85.31(4)
94.47(4)
89.49(4)
S(3)-Ru(1)-S(4)
S(2)-Ru(1)-S(3)
S(2)-Ru(1)-S(4)
P(5)-Ru(1)-S(2)
P(5)-Ru(1)-S(4)
96.58(4)
175.56(4)
87.81(3)
86.09(4)
172.95(4)
89.17(10)
83.27(10)
N(3)-Ru(1)-S(1) 171.40(10) N(3)-Ru(1)-S(2)
N(3)-Ru(1)-S(3)
N(3)-Ru(1)-P(5)
90.68(10) N(3)-Ru(1)-S(4)
93.10(10) Ru(1)-N(3)-N(4) 120.5(4)
P(1)-S(1)-Ru(1) 111.80(5)
P(3)-S(3)-Ru(1) 112.09(5)
P(2)-S(2)-Ru(1)
P(4)-S(4)-Ru(1)
111.03(5)
112.10(5)
Figure 1. Perspective view of Ru[N(Ph2PSe)2]2(PPh3) (2).
Table 5. Selected Bond Lengths (Å) and Angles (deg) for
cis-Ru[N(Ph2PS)2]2(PPh3)(C5H10NNH2) (cis-15)
in the triclinic space group P1h,10 complex 2 crystallizes in the
monoclinic space group P21/c. An ORTEP diagram of the
molecular structure of 2 is shown in Figure 1. Selected bond
distances and angles are given in Table 2. The molecule is
mononuclear with pseudo square pyramidal geometry. The
terminal PPh3 ligand occupies the apical position, and two
chelating [N(Ph2PSe)2]- ligands form the basal plane. The six-
membered RuSe2P2N rings are nonplanar and severely distorted,
displaying a twisted-boat conformation imposed by the non-
parallel orientation of the two P-Se bonds in each ligand
moiety. Each ring contains a pair of long and short Ru-Se bonds
[Ru(1)-Se(2) ) 2.5410(5) (“long”) with Ru(1)-Se(1) )
2.5269(5) (“short”); Ru(1)-Se(3) ) 2.4828(5) Å (“long”) with
Ru(1)-Se(4) ) 2.4561(5) Å (“short”)]. The average Ru-Se
distance of 2.5017(5) Å in 2 is obviously longer than the average
Ru-S distances of 2.401(2) and 2.3728(4) Å in 1. The apical
Ru-P bond length in 2 (2.2025(11) Å) is slightly shorter than
that in 1 (2.220(2) Å).10
BondLengths
Ru(1)-S(1)
Ru(1)-S(3)
Ru(1)-P(5)
N(3)-N(4)
S(2)-P(2)
S(4)-P(4)
2.4947(10)
2.4474(9)
2.2991(10)
1.405(5)
Ru(1)-S(2)
Ru(1)-S(4)
Ru(1)-N(3)
S(1)-P(1)
S(3)-P(3)
2.4312(10)
2.4051(10)
2.101(3)
2.0051(14)
2.0108(13)
2.0055(13)
2.0093(13)
BondAngles
S(1)-Ru(1)-S(2)
S(1)-Ru(1)-S(4)
S(1)-Ru(1)-S(3)
P(5)-Ru(1)-S(1)
P(5)-Ru(1)-S(3)
N(3)-Ru(1)-S(1)
90.45(4) S(3)-Ru(1)-S(4)
92.16(3) S(2)-Ru(1)-S(3)
87.42(4) S(2)-Ru(1)-S(4)
177.69(3) P(5)-Ru(1)-S(2)
91.70(4) P(5)-Ru(1)-S(4)
89.99(9) N(3)-Ru(1)-S(2)
94.45(4)
81.96(4)
175.46(3)
91.54(4)
85.77(3)
89.88(8)
93.82(8)
N(3)-Ru(1)-S(3) 171.42(8) N(3)-Ru(1)-S(4)
N(3)-Ru(1)-P(5)
P(1)-S(1)-Ru(1)
P(3)-S(3)-Ru(1)
91.19(9) Ru(1)-N(3)-N(4) 129.0(2)
111.44(5) P(2)-S(2)-Ru(1)
112.75(5) P(4)-S(4)-Ru(1)
110.62(5)
111.46(5)
Pyridine Adducts of 1 and 2. Like 1, 2 is a formally 16e
complex and reacts with Lewis bases to give octahedral 18e
adducts. Treatment of 2 in THF with excess pyridine (py) at
room temperature resulted in an orange solution, indicating the
formation of the adduct Ru[N(Ph2PSe)2]2(PPh3)(py) (3). The
31P NMR spectrum shows a doublet at δ 22.45 for [N(Ph2PSe)2]-
and a broad multiplet at δ 45.19 due to PPh3, indicative of the
trans geometry of the pyridine adduct. This is in contrast with
the reaction of 1 with py, which yielded a mixture of the cis
and trans products.10 Recrystallization from CH2Cl2/hexane
versus δ 41.03 for Cp2Y[N(Ph2PSe)2])18 systems. The positive-
ion FAB mass spectrum of 2 shows the molecular ions {Ru-
[N(Ph2PSe)2]2(PPh3)}+ and {Ru[N(Ph2PSe)2]2}+ with the char-
acteristic isotopic distribution patterns.
The solid-state structure of 2 has been established by X-ray
crystallography. Unlike the sulfide analogue 1, which crystallizes
(17) Cea-Olivares, R.; Garc´ıa-Montalvo, V.; Novosad, J.; Woollins, J. D.;
Toscano, R. A.; Espinosa-Pe´rez, G. Chem. Ber. 1996, 129, 919.
(18) Pernin, C. G.; Ibers, J. A. Inorg. Chem. 1999, 38, 5478.

5260 Inorganic Chemistry, Vol. 39, No. 23, 2000
Zhang et al.
Figure 2. Perspective view of cis-Ru[N(Ph2PSe)2](PPh3)(NH3) (cis-6).
afforded analytically pure trans-3, isolated as air-stable orange
needles. However, when a solution of trans-3 in CDCl3 was
left to stand room temperature for hours, the intensity of the
trans-3 signals decreased gradually as five new 31P signals
appeared. These five signals were attributed to cis-3 because a
similar 31P NMR spectral pattern has been observed for cis-
Ru[N(Ph2PS)2]2(PPh3)(SO2).10 Therefore it appears that reaction
of 2 with py initially gave the kinetic product trans-3, which
crystallized from the reaction mixture. In solution, trans-3 slowly
isomerized to give the thermodynamic product cis-3 (eq 1). On
electron-rich than S donor) and/or steric (the Ru-Se bond is
longer than the Ru-S bond) factors, which are not well
understood at this stage. It may also be possible that trans-4 is
the kinetic product of the reaction of 1 with SO2, as in the
formation of cis- and trans-3. The IR spectrum of 4 shows ν-
(SdO) signals at 1117 and 996 cm-1, which are lower than
those for Ru(NH3)4(SO2)Cl2 (1300 and 1130 cm-1 19
and cis-
)
Ru[N(Ph2PS)2]2(PPh3)(SO2) (1286 and 1078 cm-1),10 consistent
with the S-bound coordination mode of SO2.
Ammonia Adducts of 1 and 2. Reactions of 1 and 2 with
NH3(g) led to the formation of the corresponding NH3 adducts
Ru[N(Ph2PQ)2]2(PPh3)(NH3) (Q ) S (5), Se (6)) (eq 2), which
the basis of the integration of the py R proton signals, the
equilibrium constant for trans-3 S cis-3 in CDCl3 at room
temperature was estimated to be approximately 1.67.
SO2 Adducts of 1 and 2. As expected, electron-rich 2 has a
high affinity for π-acid ligands. Thus, bubbling SO2 gas into a
THF solution of 2 led to the formation of the SO2 adduct
Ru[N(Ph2PSe)2]2(PPh3)(SO2) (4), which was isolated as a
mixture of the cis and trans isomers according to 31P{1H} NMR
spectroscopy. This result contrasts with that of the corresponding
reaction of 1 with SO2, which yielded the structurally character-
ized cis product cis-Ru[N(Ph2PS)2]2(PPh3)(SO2) only.10 The
difference in geometry between 4 and cis-Ru[N(Ph2PS)2]2-
(PPh3)(SO2) may be due to electronic (the Se donor is more
were characterized by elemental analyses and spectroscopic
methods. Unlike the case of 3, both the cis and trans forms of
complexes 5 and 6 were observed in solution. The 31P{1H}
NMR spectrum of 6 displays seven signals at δ 18.51 (m), 21.12
(d), 22.04 (m), 22.73 (m), 27.30 (m), 48.83 (m), and 51.64 (m).
By comparison with the NMR data for trans-3, the signals at δ
21.12 (d) and 48.83 (m) were tentatively assigned to trans-6,
(19) Vogt, L. H.; Katz, J. L.; Wiberley, S. E. J. Chem. Soc. A 1965,
1157.

Ruthenium(II) Ammine and Hydrazine Complexes
Inorganic Chemistry, Vol. 39, No. 23, 2000 5261
Figure 3. Perspective view of cis-Ru[N(Ph2PS)2]2(PPh3)(t-BuNHNH2) (cis-14).
while the remaining five signals were assigned to cis-6. The
31P resonant signals for trans-5 (δ 37.89 for [N(Ph2PS)2]- and
δ 46.53 for PPh3) and cis-5 (δ 36.14, 38.58, 38.92, 40.56, 50.28)
were assigned similarly. The P-P coupling constants were not
determined owing to the poor resolution of the signals. On the
basis of integration of the NH3 protons, the cis:trans ratio for
the sample of 6 was determined to be ca. 1.85. The IR spectrum
of 6 displays the diagnostic ν(N-H) signal at 3336 cm-1 along
with the PdSe stretching vibration at 532 cm-1. The PdS
stretching vibration mode for 5 was found at 565 cm-1. The
identity of cis-6 was confirmed by the X-ray crystallographic
analysis. A perspective view of cis-6 is depicted in Figure 2;
selected bond lengths and angles are given in Table 3. The
crystal lattice of 6 was found to contain a CH2Cl2 molecule
filling a void. The geometry around the Ru atom is distorted
octahedral with PPh3 and NH3 mutually cis. The bite angles
Se(1)-Ru(1)-Se(2) (99.768(17)°) and Se(3)-Ru(1)-Se(4)
(94.861(17)°) for the RuSe2P2N rings in cis-6‚CH2Cl2 are
comparable to those in 2 and other [N(Ph2PSe)2]- complexes,
for example, 101.27(3)° in Pd(C9H12N)[N(Ph2PSe)2] and 99.3-
(1)° in Pt[N(Ph2PSe)2]2.20 The N-Ru-P angle of 95.02(9)°
deviates by more than 5° from 90° owing to the steric repulsion
between PPh3 and NH3, which also results in an elongation of
the Ru-P bond from 2.2025(11) Å in 2 to 2.2778(11) Å in
cis-6‚CH2Cl2. The Ru-N distance for cis-5‚CH2Cl2 (2.185(3)
Å) agrees well with those in [Ru(NH3)5(Me2SO)](PF6)2 (2.2169
Å)21 and 16 (2.2142(6) Å; see later). The Ru-Se distances in
cis-6‚CH2Cl2 are in the range 2.5225(5)-2.6017(5) Å, compa-
rable to those in 1 and Ru4(µ-Se)2(µ-CO)(CO)8[HN(PPh2)2]
(2.552(2)-2.579(2) Å).9
Hydrazine and Hydroxylamine Adducts of 1 and 2. The
success in isolating pyridine and ammonia adducts of 1 and 2
prompted us to prepare the hydrazine and hydroxylamine
analogues. Treatment of 1 with excess 35% aqueous hydrazine
afforded the hydrazine adduct Ru[N(PPh2S)]2(PPh3)(N2H4) (12)
(eq 3), which was found to exist in both the cis and trans forms
in solution. On the other hand, reaction of 2 with excess 35%
aqueous hydrazine afforded yellow trans-13 as the sole isolated
product. Recrystallization of trans-13 from CH2Cl2/E2O resulted
in isomerization and the formation of an orange-red crystalline
product characterized as cis-13. Unfortunately, we were unable
to obtain single crystals of cis-13 for an X-ray diffraction study.
Similarly, treatment of 2 and 3 with substituted hydrazines L
and with NH2OH yielded the respective adducts Ru[N(Ph2-
PQ)2]2(PPh3)(L) (Q ) S, L ) t-BuNHNH2 (14), C5H10NNH2
(20) Bhattacharyya, P.; Slawin, A. M. Z.; Smith, M. B. J. Chem. Soc.,
Dalton Trans. 1998, 2467.
(21) March, F. C.; Ferguson, G. Can. J. Chem. 1971, 49, 3590.

5262 Inorganic Chemistry, Vol. 39, No. 23, 2000
Zhang et al.
Figure 4. Perspective view of cus-Ru[N(Ph2PS)2]2(PPh3)(C5H10NNH2) (cis-15).
(15); Q ) Se, L ) PhCONHNH2 (7), PhNHNH2 (8), NH2OH
(9), t-BuNHNH2 (10), C5H10NNH2 (11)), which were isolated
as mixtures of their trans and cis isomers. The reaction rates
for the formation of the hydrazine adducts were found to be
dependent on the substituents on hydrazine.22 Thus, reactions
of 1 and 2 with electron-rich NH2OH, 1-aminopiperidine (C5H10-
NNH2), and t-BuNHNH2 were complete in ca. 15 min whereas
longer reaction times (ca. 1 h) were needed for PhCONHNH2
and PhNHNH2. Complexes 7-15 are air-sensitive orange or
red-orange crystalline solids. They are soluble in polar organic
solvents such as CH2Cl2 and DMF, in which they behave as
nonconductors. The IR spectra of 8-15 display characteristic
ν(N-H) bands in the 3210-3340 cm-1 region. The IR spectrum
of 7 displays ν(N-H) bands at 3211 and 3227 cm-1, along with
an intense ν(CdO) signal at 1632 cm-1, which is lower than
that for free PhCONHNH2 (1665 cm-1). For complexes 7, 8,
10, and 14, the hydrazine NH2 and NH resonant signals appear
as two broad singlets, which integrate accurately in a ratio of
1:2. For complexes 12 and 13, two nonequivalent NH signals
are observed, indicating that these complexes are mononuclear
and that the hydrazine binds to Ru in an η1 fashion. The 31P-
{1H} NMR spectra of complexes 7-11, 14, and 15 each show
seven signals, indicative of the presence of the trans and cis
isomers for these complexes in solution.
respectively). After the solution was allowed to stand for 1 day
at room temperature, five additional 31P signals attributable to
cis-13 appeared. Thus, it appears that, as in the formation of
the pyridine adduct, trans-13 was the kinetic product while cis-
13 was the thermodynamic product for the reaction between 2
and hydrazine. The yield of trans-13 was enhanced if a large
excess of hydrazine was used. Recrystallization of 13 from CH2-
Cl2/hexane afforded orange crystals of pure cis-13, along with
a yellow powder, presumably containing trans-13, which has
not yet been isolated in a pure form.
X-ray-quality single crystals of cis-14‚CH2Cl2 and cis-15 were
easily obtained by recrystallization of the complexes from CH2-
Cl2/E2O. Their solid-state structures were then established by
X-ray crystallography. The molecular structures of cis-14 and
cis-15 are shown in Figures 3 and 4, respectively. Tables 4 and
5 list the selected bond distances and angles for cis-14‚CH2Cl2
and cis-15, respectively. For both structures, the geometry
around Ru is pseudooctahedral with PPh3 cis to the hydrazine
ligand. The Ru-N bond lengths in cis-14‚CH2Cl2 (2.152(3) Å)
and cis-15 (2.101(3) Å) are consistent with an Ru-N(sp3) dative
bond. The Ru-N-N bond angles in cis-14‚CH2Cl2 (120.5(4)°)
and cis-15 (129.0(2)°) are somewhat opened compared to the
tetrahedral value. The Ru-N-N angle in cis-15 is larger than
that in cis-13‚CH2Cl2, possibly due to the steric bulk of the
piperidine moiety. For this reason, the N-N bond length (1.451-
(8) Å) for cis-14‚CH2Cl2 is slightly longer than that for cis-15
(1.405(2) Å). The N-N bond lengths for both complexes are
comparable to that for [(η6-C6Me6)Ru(S-2,6-C6H3Me2)2(NH2-
NH2)] (1.378(10) Å),23 indicating that the N-N bond is a single
bond. It is noteworthy that the Ru-P bond lengths in cis-14‚
The course of reaction between 2 and hydrazine was followed
by 31P NMR spectroscopy. Treatment of 2 with a slight excess
of 35% aqueous hydrazine in CDCl3 initially yielded yellow
trans-13 (δ 42.07 and 89.51 due to [N(Ph2PSe)2]- and PPh3,
(22) Albertin, G.; Antoniutti, S.; Bacchi, A.; Bordignon, E.; Dolcetti, P.
M.; Pelizzi, G. J. Chem. Soc., Dalton Trans. 1997, 4435.

Ruthenium(II) Ammine and Hydrazine Complexes
Inorganic Chemistry, Vol. 39, No. 23, 2000 5263
Figure 5. Perspective view of trans-Ru[N(Ph2PS)2]2(NH3)(H2O) (16).
CH2Cl2 (2.2845(10) Å) and cis-15 (2.2991(10) Å) are somewhat
longer than that found in 1 (2.220(2) Å).10 This elongation may
be due to the steric bulk and/or electron-donating properties of
the coordinated t-BuNHNH2 and C5H10NNH2 ligands. The
Ru-S bond lengths for the two complexes are normal by
comparison with other related complexes in the literature.8,10,24
Reaction of 1 with hydrazine monohydrate. Interestingly,
treatment of 1 with hydrazine monohydrate (N2H4‚H2O) led to
the isolation of yellow cis-Ru[N(Ph2PS)2]2(PPh3)(NH3) (cis-5)
and red trans-Ru[N(Ph2PS)2]2(NH3)(H2O) (16) eq 4), which
a perspective view of 16; selected bond lengths and angles are
listed in Table 6. The ruthenium center has an octahedral
coordination environment with the NH3 and H2O ligands
mutually trans. The bite angles S(1)-Ru(1)-S(2) and S(3)-
Ru(1)-S(4) in 16 are substantially larger than those in cis-14‚
CH2Cl2 and cis-15. The Ru-S bond lengths in 16 agree well
with those in cis-14‚CH2Cl2 and cis-15. The Ru-O bond
distance 2.118(4) Å is similar to that observed for [RuTp(H2O)-
(P(i-Pr2)Me)2](OTf) [2.142(6) Å; Tp ) hydrotris(pyrazolyl)-
borate].26 The Ru-N bond distance of 2.142(6) Å is in the
normal range for a Ru-N single bond.
Electrochemistry. Formal potentials of the RuII[N(Ph2PQ)2]
complexes were determined by cyclic voltammetry. The cyclic
voltammogram of 2 in CH2Cl2 shows a reversible couple at E1/2
) -0.17 V vs Cp2Fe+/0, which was assigned as the metal-
centered Ru(III/II) couple because HN(Ph2PSe)2 is redox
inactive at this potential. It is quite surprising that the Ru(III/
II) potential for 2 is similar to that for the sulfide analogue 1
(-0.24 V) because one might expect that selenide is a better
π-donor than sulfide and thus should be more capable of
stabilizing the Ru(III) state. The Ru(III/II) couple for the
pyridine adduct 3 occurs at E1/2 ) -0.21 V, while those for
the ammine and hydrazine adducts of 2 were found in the range
of -0.19 to -0.28 V, indicating that the Ru(III) states for these
complexes are stabilized by coordination to N-donor ligands.
No Ru(III/II) oxidation was found for the SO2 complex 4
because the Ru(II) state is stabilized by strongly π-acidic SO2
ligand.
1
were characterized by mass spectrometry, H NMR spectros-
copy, and elemental analyses. The ammine ligands in cis-5 and
16 apparently came from the hydrazine hydrate (either via a
redox reaction of hydrazine or from the ammonia impurity in
hydrazine). It may be noted that 1e reduction of hydrazine to
+
give NH3 or NH4 and metal-mediated decomposition of
hydrazine to give metal ammine complexes are well docu-
mented.25 The difference in reactivity toward 1 between aqueous
hydrazine and hydrazine hydrate may be due to a concentration
effect. The IR spectrum of 16 shows a broad band at 3422 cm-1
and a weak band at 3284 cm-1, which were assigned as the
O-H and N-H stretches, respectively. The solid-state structure
of 16 was established by X-ray crystallography. Figure 5 shows
Oxidation of Ru(II) Hydrazine Complexes. Oxidation of
the hydrazine ligand to give 1,2-diazene (NHdNH) complexes
is well documented.5,6 Sellmann and co-workers reported the
preparations of the diazene complexes [(µ-NHNH){Fe(PR3)-
(‘S4’)}2] (R ) Me, Et, Ph) and [{Ru(‘S4’)(PPh3)}2(µ-NHNH)]
(‘S4’ ) [(SC6H4SCH2)2NH]2-) by air oxidation of the corre-
(23) Mashima, K.; Kaneyoshi, H.; Kaneko, S.; Tani, K.; Nakamura, A.
Chem. Lett. 1997, 569.
(24) (a) Maiti, R.; Shang, M.; Lappin, A. G. Chem. Commun. 1999, 2349.
(b) Kawano, M.; Uemura, H.; Watanabe, T.; Matsumoto, K. J. Am.
Chem. Soc. 1993, 115, 2068.
(25) (a) Pickett, C. J. J. Biol. Inorg. Chem. 1996, 1, 601. (b) Sellmann, D.;
Sutter, J. J. Biol. Inorg. Chem. 1996, 1, 587. (c) Stanbury, D. M. Prog.
Inorg. Chem. 1998, 47, 511.
(26) Tenorio, M. A. J.; Tenorio, M. J.; Puerta, M. C.; Valerga, P. J. Chem.
Soc., Dalton Trans. 1998, 3601.

5264 Inorganic Chemistry, Vol. 39, No. 23, 2000
Zhang et al.
sponding hydrazine precursors.6 Hillhouse and co-workers
successfully isolated diazene complexes of Os(II) and W(II) by
Pb(OAc)4 oxidation of the corresponding hydrazine complexes
at low temperature (-78 °C).5 However, an attempt to prepare
a ruthenium(II) diazene complex by Pb(IV) oxidation of 13
under similar reaction conditions led to the isolation of an
intractable paramagnetic dark solid. The IR spectrum of this
dark solid displayed characteristic bands for [N(Ph2PSe)2]- and
PPh3, but neither ν(N-H) nor ν(NdN) was observed. When a
solution of 12 in CH2Cl2 was left to stand in air overnight, a
yellow-green solution resulted. Slow evaporation of the yellow-
green solution yielded an orange crystalline product analyzed
as Ru[N(Ph2PS)2](PPh3)(N2H2) (18) along with an uncharac-
terized dark green paramagnetic species. The IR spectrum of
18 displays ν(N-H) signals at 3341 and 3330 cm-1, which are
slightly higher than those for 12, along with a band at 1572
cm-1 assignable to ν(NdN). The solid-state structure of 18 was
determined and was found to be consistent with the formulation
of an Ru-NHdNH species.27 However, because of disorder in
the crystal structure, the proposed diazene formulation for 18
could not be definitively confirmed.
were found to be dependent on the nature of the hydrazine
reagent used. Treatment of 2 with 35% aqueous hydrazine gave
a ruthenium hydrazine complex, while 2 reacted with hydrazine
hydrate to give a mixture of ruthenium(II) ammine phosphine
and ammine aquo complexes. We believe that the chemistry of
dinitrogen, diazene, and hydrazine coordinated to ruthenium is
extensive and will provide further insights into the mechanism
of abiological nitrogen fixation. Investigations in this area are
under way.
Acknowledgment. We thank The Croucher Foundation and
The Hong Kong University of Science and Technology for
support.
Supporting Information Available: X-ray crystallographic files,
in CIF format, for the structure determinations of 2, cis-6‚CH2Cl2, cis-
14‚CH2Cl2, cis-15, 16, and 18. This material is available free of charge
via the Internet at http://pubs.acs.org.
IC000291C
(27) The solid-state structure of complex 18 is consistent with the
formulation of the Ru(II) diazene species cis-Ru[N(Ph2PS)2](PPh3)-
(NHdNH). Crystal data for 18, C66H59N4P5S4Ru: a ) 10.663(8) Å,
b ) 28.496(6) Å, c ) 20.446(4) Å, â ) 102.48(3)°, V ) 6065(3) Å3,
monoclinic, P21/n space group, Z ) 4, Fcalcd ) 1.413 g cm-3, µ )
5.73 cm-1, no. of data ) 8137, R ) 0.068, Rw ) 0.081. The
uncoordinated nitrogen N(4) of the N2H2 ligand was found to be 50:
50 disordered. The observed average Ru-N(3)-N(4) angle of 134°
is larger than those for hydrazine complexes cis-14 and cis-15 but is
comparable to that for known diazene complexes such as [Os(NHd
NH)(CO)2(PPh3)2Br][OTf)] (135.9(10)°).5c The Ru-N(3) and average
N(3)-N(4) distances are 2.07(2) and 1.235 Å, respectively.
Summary
We synthesized a series of hydrazine complexes of ruthenium-
(II) in sulfur- and selenium-rich coordination environments.
NMR spectroscopy revealed that these complexes exist as a
mixture of their cis and trans isomers in solution. The products
of the reactions between Ru[N(Ph2PQ)2]2(PPh3) and hydrazine