Synthesis, crystal structures, and reactivity of osmium(II) and -(IV) complexes containing a dithioimidodiphosphinate ligand

Article abstract of DOI:10.1021/ic070048e

Reduction of trans-[OsL₂(O)₂] (1) (L^- = [N(i-Pr₂PS)₂]^-) with hydrazine hydrate afforded a dinitrogen complex 2, possibly [OsL₂(N₂)(solv)] (solv = H₂O or THF), which reacted with RCN, R′NC, and SO₂ to give trans-[OsL₂(RCN)₂] (R = Ph (3), 4-tolyl (4), 4-t-BuC₆H₄ (5)), trans-[OsL ₂(R′NC)₂] (R′ = 2,6-Me₂C ₆H₃ (xyl) (6), t-Bu (7)), and [Os(L)₂(SO ₂)(H₂O)] (8) complexes, respectively. Protonation of compounds 2, 3, and 6 with HBF₄ led to formation of dicationic trans-[Os(LH)₂(N₂)(H₂O)][BF₄] ₂ (9), trans-[Os(LH)₂(PhCN)₂][BF ₄]₂ (10), and trans-[Os(LH)₂(xylNC) ₂][BF₄]₂ (11), respectively. Treatment of 1 with phenylhydrazine and SnCl₂ afforded trans-[OsL₂(N ₂Ph)₂] (12) and trans-[OsL₂Cl₂] (13), respectively. Air oxidation of compound 2 in hexane/MeOH gave the dimethoxy complex trans-[OsL₂(OMe)₂] (14), which in CH₂Cl₂ solution was readily air oxidized to 1. Compound 1 is capable of catalyzing aerobic oxidation of PPh₃, possibly via an Os(IV) intermediate. The formal potentials for the Os-L complexes have been determined by cyclic voltammetry. The solid-state structures of compounds 4, 6, cis-8, 13, and 14 have been established by X-ray crystallography.

Full text of DOI:10.1021/ic070048e

Inorg. Chem. 2007, 46, 5754−5762
Synthesis, Crystal Structures, and Reactivity of Osmium(II) and -(IV)
Complexes Containing a Dithioimidodiphosphinate Ligand
Wai-Man Cheung,† Qian-Feng Zhang,‡ Ian D. Williams,† and Wa-Hung Leung*,†
Department of Chemistry, The Hong Kong UniVersity of Science and Technology, Clear Water
Bay, Kowloon, Hong Kong, People’s Republic of China, and Department of Applied Chemistry,
Anhui UniVersity of Technology, Ma’anshan, Anhui 243002, People’s Republic of China
Received January 11, 2007
Reduction of trans-[OsL2(O)2] (1) (L-
possibly “[OsL2(N2)(solv)]” (solv H2O or THF), which reacted with RCN, R
(RCN)2] (R Ph (3), 4-tolyl (4), 4-t-BuC6H4 (5)), trans-[OsL2(R NC)2] (R′ ) 2,6-Me2C6H3 (xyl) (6), t-Bu (7)), and
)
[N(i-Pr2PS)2]-) with hydrazine hydrate afforded a dinitrogen complex 2,
)
′
NC, and SO2 to give trans-[OsL2-
)
′
[Os(L)2(SO2)(H2O)] (8) complexes, respectively. Protonation of compounds 2, 3, and 6 with HBF4 led to formation
of dicationic trans-[Os(LH)2(N2)(H2O)][BF4]2 (9), trans-[Os(LH)2(PhCN)2][BF4]2 (10), and trans-[Os(LH)2(xylNC)2][BF4]2
(11), respectively. Treatment of 1 with phenylhydrazine and SnCl2 afforded trans-[OsL2(N2Ph)2] (12) and trans-
[OsL2Cl2] (13), respectively. Air oxidation of compound 2 in hexane/MeOH gave the dimethoxy complex trans-
[OsL2(OMe)2] (14), which in CH2Cl2 solution was readily air oxidized to 1. Compound 1 is capable of catalyzing
aerobic oxidation of PPh3, possibly via an Os(IV) intermediate. The formal potentials for the Os−L complexes have
been determined by cyclic voltammetry. The solid-state structures of compounds 4, 6, cis-8, 13, and 14 have been
established by X-ray crystallography.
Introduction
to12,13 ligands are well-known, the catalytic activity of the
OsS4 core has not been well explored. This is in contrast
with Os compounds with polydentate nitrogen ligands, e.g.,
porphyrins, tris(pyrazolyl)borate, tetraza macrocycles, and
polypyridyl, which display rich redox and catalytic chem-
istry.14
Transition metal sulfur systems have attracted much
attention due to their significance in catalysis, materials
science, and biology.1,2 To gain insight into the mechanisms
of sulfur-containing catalysts, much effort has been devoted
to develop molecular models based on metal thiolate and
sulfido complexes.3-5 Of special interest are group 8 thiolato
compounds due in part to the finding that binary noble metal
sulfides, notably RuS2, are highly active in hydrodesulfur-
ization processes.6 Although sulfur-rich Os complexes con-
taining thiophenolato,7-9 dithiocarbamato,10,11 and dithiola-
Dichalcogenoimidodiphosphinates [N(R2PQ)2]- (R ) alkyl
or aryl; Q ) O, S, or Se) (Chart 1), which are considered as
(6) (a) Chianelli, R. R. Catal. ReV.sSci. Eng. 1984, 26, 361. (b) Kabe,
T.; Ishihara, A.; Qian, W. Hydrodesulfurization and Hydrodenitro-
genation; Wiley-VCH: Chichester, U.K., 1999.
(7) (a) Dilworth, J. R.; Hu, J. AdV. Inorg. Chem. 1994, 40, 411. (b) Torrens,
* To whom correspondence should be addressed. E-mail: chleung@
ust.hk.
H. Coord. Chem. ReV. 2000, 196, 331.
(8) (a) Koch, S. A.; Millar, M. J. Am. Chem. Soc. 1983, 105, 3362. (b)
Satsangee, S. P.; Hain, J. H., Jr.; Cooper, P. T.; Koch, S. A. Inorg.
Chem. 1992, 31, 5160.
† The Hong Kong University of Science and Technology.
‡ Anhui University of Technology.
(1) (a) Burgess, B. K.; Lowe, D. J. Chem. ReV. 1996, 96, 2983. (b) Eady,
R. R. Chem. ReV. 1996, 96, 3013. (b) Howard, J. B.; Rees, D. C.
Chem. ReV. 1996, 96, 2965. (c) Beinert, H.; Holm, R. H.; Mu¨nck, E.
Science 1997, 277, 653.
(2) Stiefel, E. I. 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 1 and references cited therein.
(3) (a) Sellmann, D.; Sutter, J. Acc. Chem. Res. 1997, 30, 460. (b)
Sellmann, D.; Utz, J.; Blum, N.; Heinemann, F. W. Coord. Chem.
ReV. 1999, 190-192, 607. (c) Reference 1, Chapter 5.
(4) Rauchfuss, T. B. Inorg. Chem. 2004, 43, 14.
(9) (a) Hills, A.; Hughes, D. L.; Richards, R. L.; Arroyo, M.; Gruz-Garritz,
D.; Torrens, H. J. Chem. Soc., Dalton Trans. 1991, 1281. (b) Arroyo,
M.; Chamizo, J. A.; Hughes, D. L.; Richards, R. L.; Roman, P.; Sosa,
P.; Torrens, H. J. Chem. Soc., Dalton Trans. 1994, 1819.
(10) (a) Maheu, L. J.; Miessler, G. L.; Berry, J.; Burow, M.; Pignolet, L.
H. Inorg. Chem. 1983, 22, 405. (b) Wheeler, S. H.; Pignolet, L. H.
Inorg. Chem. 1980, 19, 972. (c) Given, K. W.; Wheeler, S. H.; Jick,
B. S.; Maheu, L. J.; Pignolet, L. H. Inorg. Chem. 1979, 18, 1261.
(11) (a) Menon, M.; Pramanik, A.; Bag, N.; Chakravorty, A. J. Chem. Soc.,
Dalton Trans. 1995, 1543. (d) Pramanik, A.; Bag, N.; Chakravorty,
A. J. Chem. Soc., Dalton Trans. 1993, 237. (e) Schofield, M. H.; Kee,
T. P.; Anhaus, J. T.; Schrock, R. R.; Johnson, K. H.; Davis, M. W.
Inorg. Chem. 1991, 30, 3595.
(5) DuBois, M. R. Polyhedron 1997, 16, 3089.
5754 Inorganic Chemistry, Vol. 46, No. 14, 2007
10.1021/ic070048e CCC: $37.00
© 2007 American Chemical Society
Published on Web 06/13/2007

Osmium Complexes with a Dithioimidodiphosphinate
Chart 1
a Perkin-Elmer 16 PC FT-IR spectrophotometer. Magnetic moments
of paramagnetic compounds were determined by Evans method20
at room temperature. 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), respectively, and the scan rate was
100 mV s-1. Formal potentials (E1/2) were measured in CH2Cl2
solutions with 0.1 M [n-Bu4N][PF6] as supporting electrolyte and
reported with reference to the ferrocenium-ferrocene couple
(Cp2Fe+/0). Elemental analyses were preformed by Medac Ltd.,
Surrey, U.K. The dioxo compound trans-[OsL2(O)2] (1) was
prepared as described elsewhere.17
chalcogen analogues of acetylacetonates, can bind to metal
ions with a high degree of electronic and geometric flex-
ibilities.15
Although [N(R2PQ2)2]- is known to form stable complexes
with a range of main group and transition metals, the
coordination chemistry of Os-N(R2PQ2)2 is not well devel-
oped.16,17 We are particularly interested in the isopropyl-
substituted ligand [N(i-Pr2PS)2]- (denoted as L-)18 due to
its high basicity and good solubility in organic solvents.
Metal complexes with L- are known to exhibit interesting
structural chemistry and reactivity.18,19 Previously, we re-
ported that reduction of trans-[OsL2(O)2] (1) with hydrazine
gave a dinitrogen species, possibly “[OsL2(N2)(solv)]” (solv
) THF or water) (2),17 which may serve as a useful starting
material for Os-L compounds. Herein, we describe the
substitution reactions and air oxidation of compound 2 and
the reduction of compound 1 with phenyl hydrazine, SnCl2,
and phosphines. The crystal structures and formal potentials
of Os(II) and -(IV) complexes with L- have been determined.
Preparation of trans-[Os(L)2(RCN)2] (R ) Ph (3), Tolyl (4),
4-t-BuC6H4 (5)). The dinitrogen complex 2 was prepared as
described previously.17 To compound 1 (60 mg, 0.071 mmol) in
THF (10 mL) was added hydrazine hydrate (0.1 mL), and the
mixture was stirred for 2 h. The solvent was pumped off, and
the residue was extracted into hexane (5 mL). To this hexane
solution of compound 2 was added RCN (0.21 mmol), and the
reaction mixture was stirred at room temperature for 30 h. The
solvent was removed, and the residue was washed with cold hexane
(-78 °C) and extracted with Et2O (for compound 3), hexane/Et2O
(1:1 v/v) (for compound 4), or hexane/CH2Cl2 (1:1 v/v) (for
compound 5). Concentration and cooling at -10 °C afforded brown
crystals.
3: 15 mg, 21% (based on compound 1 used). 1H NMR (C6D6):
δ 1.48 (m, 48H, (CH3)2CH), 2.49 (m, 8H, (CH3)2CH), 7.08-7.14
(m, 6H, Ho and Hp), 7.66-7.71 (m, 4H, Hm). 31P{1H} NMR
(C6D6): δ 58.73 (s). IR (KBr, cm-1): 2175 (νCN). Anal. Calcd for
C40H70N4OsP4S4: C, 44.7; H, 6.5; N, 5.5. Found: C, 44.5; H, 6.5;
N, 5.4.
Experimental Section
General Considerations. Solvents were purified by standard
procedures and distilled prior to use. All manipulations were carried
out under nitrogen by standard Schlenk techniques. NMR spectra
were recorded on a Bruker ALX 300 spectrometer operating at 300,
121.5, and 282.5 MHz for 1H, 31P, and 19F, respectively. Chemical
shifts (δ, ppm) were reported with reference to SiMe4 (1H), H3PO4
(31P), and CF3C6H5 (19F). Infrared spectra (KBr) were recorded on
4: 16 mg, 22% (based on compound 1 used). 1H NMR (C6D6):
δ 1.57 (m, 48H, (CH3)2CH), 2.10 (s, 6H, CH3), 2.51 (m, 8H,
(CH3)2CH), 6.93 (d, J ) 8.2 Hz, 4H, Ho), 7.64 (d, J ) 8.2 Hz, 4H,
Hm). 31P{1H} NMR (C6D6): δ 58.72 (s). IR (KBr, cm-1): 2177
(νCN). Anal. Calcd for C40H70N4OsP4S4: C, 45.8; H, 6.7; N, 5.3.
Found: C, 45.3; H, 6.8; N, 5.3.
5: 22 mg, 28% (based on compound 1 used). 1H NMR (C6D6):
δ 1.27 (s, 18H, t-Bu), 1.56 (m, 48H, (CH3)2CH), 2.50 (m, 8H,
(CH3)2CH), 7.29 (d, J ) 8.4 Hz, 4H, Ho), 7.76 (d, J ) 8.4 Hz, 4H,
Hm). 31P {1H} NMR (C6D6): δ 58.67 (s). IR (KBr, cm-1): 2175
(νCN). Anal. Calcd for C46H82N4OsP4S4: C, 48.7; H, 7.3; N, 4.9.
Found: C, 48.4; H, 7.5; N, 4.8.
(12) (a) Sellmann, D.; Prakash, R.; Heinemann, F. W. Dalton Trans. 2004,
3991. (b) Sellmann, D.; Engl. K.; Gottschalk-Gaudig, T.; Heinemann,
F. W. Eur. J. Inorg. Chem. 1999, 333. (c) Sellmann, D.; Hennige, A.
C.; Heinemann, F. W. Eur. J. Inorg. Chem. 1998, 819. (d) Sellmann,
D.; Wemple, M. W.; Donaubauer, W.; Heinemann, F. W. Inorg. Chem.
1997, 36, 1397.
(13) (a) Leung, W.-H.; Wu, M.-C.; Che, C.-M.; Wong, W.-T.; Chin, K.-F.
J. Chem. Soc., Dalton Trans. 1994, 2519. (b) Leung, W.-H.; Chim, J.
L. C.; Wong, W.-T. Inorg. Chem. 1998, 37, 6382. (c) Reinert, W. A.;
Shapley, P. A. Inorg. Chim. Acta 1998, 267, 335.
(14) Che, C.-M.; Lau, T. C. In ComprehensiVe Coordination Chemistry
II; McCleverty, J. A., Meyer, T. J., Eds.; Elsevier Pergamon:
Amsterdam, 2004; Vol. 5, Chapter 5.6, p 733.
(15) (a) Haiduc, I. In ComprehensiVe Coordination Chemistry II; McClev-
erty, J. A., Meyer, T. J., Eds.; Elsevier Pergamon: Amsterdam,
2004; Vol. 1, p 323 and references cited therein. (b) Ly, T. Q.;
Woollins, J. D. Coord. Chem. ReV. 1998, 176, 451 and references
cited therein. (c) Silvestru, C.; Drake, J. E. Coord. Chem. ReV. 2001,
223, 117.
(16) (a) Ho, E. N. M.; Wong, W.-T. J. Chem. Soc., Dalton Trans. 1997,
915. (b) Parr, J.; Smith, M. B.; Elsegood, M. R. J. J. Organomet.
Chem. 2002, 664, 85.
(17) Zhang, Q.-F.; Lau, K.-K.; Chim, J. L. C.; Wong, T. K. T.; Wong,
W.-T.; Williams, I. D.; Leung, W.-H. J. Chem. Soc. Dalton Trans.
2000, 3027.
(18) (a) Cupertino, D.; Keyte, R.; Slawin, A. M. Z.; Williams, D. J.;
Woollins, J. D. Inorg. Chem. 1996, 35, 2695. (b) Cupertino, D.;
Birdsall, D. J.; Slawin, A. M. Z.; Woollins, J. D. Inorg. Chim. Acta
1999, 290, 1. (c) Birdsall, D. J.; Slawin, A. M. Z.; Woollins, J. D.
Polyhedron 2001, 20, 125.
Preparation of trans-[OsL2(R′NC)2] (R′ ) 2,6-Me2C6H3 or
Xyl (6), t-Bu (7)). To the above-described hexane solution of 2
was added 2 equiv of R′NC, and the reaction mixture was stirred
at room temperature for 30 h. The solvent was removed in vacuo,
and the residue was extracted with hexane (R ) xyl) or CH2Cl2/
hexane (R ) t-Bu). Concentration and cooling at -10 °C afforded
yellow crystals.
6: 21 mg, 28% (based on 1 used). 1H NMR (C6D6): δ 1.34 (m,
48H, (CH3)2CH), 2.59 (m, 8H, (CH3)2CH), 2.99 (s, 12H, CH3),
7.00-7.12 (m, 6H, phenyl protons). 31P{1H} NMR (C6D6): δ 59.04
(s). IR (KBr, cm-1): 2007, 2038 (νCN). Anal. Calcd for C42H74N4-
OsP4S4: C, 46.8; H, 6.9; N, 5.2. Found: C, 46.8; H, 6.9; N, 4.9.
7: 12 mg, 17% (based on 1 used). 1H NMR (C6D6): δ 1.54 (m,
48H, (CH3)2CH), 1.66 (s, 18H, t-Bu), 2.52 (m, 8H, (CH3)2CH).
31P{1H} NMR (C6D6): δ 58.28 (s). IR (KBr, cm-1): 2033 (νCN).
Anal. Calcd for C34H74N4OsP4S4: C, 41.6; H, 7.6; N, 5.7. Found:
C, 41.6; H, 7.7; N, 5.5.
(19) Zhang, Q.-F.; Zheng, H.; Wong, W.-Y.; Williams, I. D.; Leung, W.-
H. Inorg. Chem. 2000, 39, 5255.
(20) Evans, D. J. Chem. Soc. 1959, 2003.
Inorganic Chemistry, Vol. 46, No. 14, 2007 5755

Cheung et al.
Preparation of [OsL2(SO2)(H2O)] (8). Sulfur dioxide was
bubbled into the above-described hexane solution of 2 for 3 min,
during which the color changed from purple to reddish brown. The
reaction mixture was stirred at room temperature for 30 min and
evaporated to dryness. Recrystallization from CH2Cl2/hexane (1:2,
v/v) at -10 °C afforded dark brown crystals. Yield: 19 mg, 30%
IR (KBr, cm-1): 1530 (s) (νNN). Anal. Calcd for C36H66N6-
OsP4S4‚CH2Cl2: C, 41.1; H, 6.3; N, 7.9. Found: C, 41.0; H, 6.7;
N, 7.9.
Preparation of trans-[OsL2Cl2] (13). To a solution of compound
1 (60 mg, 0.071 mmol) in THF (10 mL) was added 2.5 equiv of
SnCl2 (34 mg, 0.18 mmol) at 0 °C. The reaction mixture was stirred
at room temperature for 20 min, during which the color of solution
changed from red to green and finally purple. The solvent was
removed, and the residue was extracted into toluene. Evaporation
of the solvent afforded a dark solid, which was recrystallized from
CH2Cl2/hexane to give dark purple crystals. Yield: 26 mg, 42%.
1H NMR (CDCl3): δ 1.23 (m, 2H, (CH3)2CH), 3.40 (m, 24H,
(CH3)2CH), 3.64 (m, 6H, (CH3)2CH), 4.69 (m, 24H, (CH3)2CH).
µeff (CDCl3) ) 1.8 µB. Anal. Calcd for C24H56Cl2N2OsP4S4: C,
32.5; H, 6.4; N, 3.2. Found: C, 32.3; H, 6.4; N, 3.0.
Preparation of trans-[OsL2(OMe)2] (14). To the above-
described hexane solution of compound 2 was added 5 mL of
methanol, and the mixture was stirred vigorously under nitrogen
until a homogeneous mixture was resulted. Upon exposure to air,
an orange solution was formed. Slow evaporation at room temper-
ature overnight afforded orange crystals, which were collected and
washed with hexane. Yield: 25 mg, 40% (based on compound 1
used). 1H NMR (C6D6): δ 2.44 (m, 24H, (CH3)2CH), 2.74 (m, 24H,
(CH3)2CH), 3.84 (m, 8H, (CH3)2CH), 42.90 (s, 6H, OCH3). 31P-
{1H} NMR (C6D6): δ 34.65 (s). µeff (CDCl3/CD3OD, 1:1, v/v) )
1.6 µB. Anal. Calcd for C26H62N2O2OsP4S4: C, 35.6; H, 7.1; N,
3.2. Found: C, 35.6; H, 7.2; N, 3.2.
1
(based on compound 1 used). H NMR (C6D6): δ 1.25-1.68 (m,
48H, (CH3)2CH), 2.02 (m, 4H, (CH3)2CH), 2.54 (m, 4H, (CH3)2CH).
31P{1H} NMR (C6D6): δ 61.30 (d, J ) 24 Hz, cis isomer), 59.37
(br s, cis isomer), 59.16 (br s, cis isomer), 58.49 (s, trans isomer),
56.40 (d, J ) 24 Hz, cis isomer). In addition, a weak signal at δ
58.77 (s), possibly due to a trans-Os(L)2 species, was observed in
the 31P{1H} NMR spectrum. IR (cm-1, KBr): 1266 (νSO). Anal.
Calcd for C24H58N2O3OsP4S5‚1/2CH2Cl2‚H2O: C, 30.7; H, 6.4; N,
2.9. Found: C, 30.6; H, 6.6; N, 3.3. We were not able to obtain
satisfactory nitrogen analysis of the compound.
Preparation of [Os(HL)2(N2)(H2O)](BF4)2 (9). The above-
described hexane solution of compound 2 was evaporated to
dryness, and the residue was redissolved in 10 mL of Et2O. To the
solution was added 2 equiv of HBF4 (20 µL of a 54% in Et2O,
0.14 mmol) at 0 °C, at which the mixture was stirred for 30 min.
The red precipitate was collected, washed with Et2O, and dried in
vacuo. Yield: 35 mg (80% based on 2). The compound was found
to be very air sensitive in solution. IR (KBr, cm-1): 2044 (νNN).
Anal. Calcd for C24H60B2F8N4OOsP4S4‚H2O: C, 27.3; H, 5.9; N,
5.3. Found: 27.1; H, 6.0; N, 5.0.
Preparation of trans-[Os(HL)2(PhCN)2](BF4)2 (10). To a
solution of compound 3 (30 mg, 0.029 mmol) in Et2O (15 mL)
was added HBF4 (9 µL of a 54% solution in Et2O, 0.065 mmol) at
-78 °C, and the mixture was stirred at room temperature for 15
min. The orange precipitate was collected, washed with Et2O, and
recrystallized from CH2Cl2/Et2O to afford a yellowish orange
Preparation of cis-[OsL2(PMePh2)2] (15). To a solution of
compound 1 (60 mg, 0.071 mmol) in THF (15 mL) was added 4
equiv of PMePh2, and the mixture was stirred at room temperature
for 30 h. The solvent was removed, and the orange solid was
extracted with Et2O/hexane (1:1, v/v). Concentration and cooling
at -10 °C afforded orange crystals along with a white solid
identified as OPMePh2, which was removed by cold acetone.
Yield: 21 mg, 24%. 1H NMR (C6D6): δ 1.34-1.70 (m, 48H,
1
microcrystalline solid. Yield: 19 mg, 54%. H NMR (CDCl3): δ
1.31 (m, 48H, (CH3)2CH), 2.87 (m, 8H, (CH3)2CH), 6.30 (br s,
2H, NH), 7.61-7.64 (m, 10H, phenyl protons). 31P{1H} NMR:
89.38 (s). 19F{1H} NMR (CDCl3): δ -149.79 (s). IR (KBr, cm-1):
2194 (νCN), 3152 (νNH). Anal. Calcd for C38H68B2F8N4OsP4S4:
C, 38.1; H, 5.7; N, 4.7. Found: C, 38.2; H, 5.8; N, 4.5.
2
(CH3)2CH), 2.15 (m, 4H, (CH3)2CH), 2.66 (d, JPH ) 8.0 Hz, 6H,
Me), 2.71 (m, 2H, (CH3)2CH), 3.61 (m, 2H, (CH3)2CH), 7.26 (m,
12H, phenyl protons), 7.99 (m, 8H, phenyl protons). 31P{1H} NMR
(C6D6): δ -42.61 (m, PMePh2), 49.16 (m, L), 50.10 (m, L). Anal.
Calcd for C50H82N2OsP6S4‚1/2Et2O: C, 49.9; H, 7.0; N, 2.2;
Found: C, 49.9; H, 6.9; N, 2.1.
Os-Catalyzed Aerobic Oxidation of PPh3. A mixture of PPh3
(15 mg, 0.059 mmol) and compound 1 (5 mg, 0.0059 mmol) in
CHCl3 (5 mL) was stirred under 1 atm pressure of oxygen at room
temperature for 2 d. The yield of triphenylphosphine oxide was
determined to be 92% by 31P NMR spectroscopy using PPh4Cl as
internal standard.
X-ray Crystallographic Analysis. Crystallographic data and
experimental details for compounds 4, 6, cis-8, 13, and 14 are
summarized in Table 1. Intensity data were collected on a Bruker
SMART APEX 1000 CCD diffractometer using graphite-mono-
chromated Mo KR radiation (λ ) 0.710 73 Å). The collected frames
were processed with the software SAINT.21 Structures were solved
by the direct methods and refined by full-matrix least-squares on
F2 using SHELXL22 software package. In 6, the carbon atoms
C(37)-C(42) and C(27) in the isopropyl groups were found to be
disordered and were split into two positions with occupancies of
0.5 each. Selected bond lengths and angles for compounds 4, 6,
13, and 14 are listed in Table 2, and those for cis-8, in Table 3.
Preparation of trans-[Os(HL)2(xylNC)2](BF4)2 (11). This com-
pound was prepared similarly as for compound 11 by protonation
of compound 6 (30 mg, 0.028 mmol) in Et2O (15 mL) with HBF4
(8 µL of a 54% solution in Et2O, 0.061 mmol). Recrystallization
from CH2Cl2/Et2O afforded pale orange crystals. Yield: 21 mg,
60%. 1H NMR (CDCl3): δ 1.17 (m, 48H, (CH3)2CH), 2.59 (s, 12H,
CH3), 2.75 (m, 8H, (CH3)2CH), 6.36 (br. s, 2H, NH), 7.22 (m, 6H,
phenyl protons). 31P{1H} NMR (CDCl3): δ 89.80 (s). 19F{1H} NMR
(CDCl3): δ -149.62. IR (KBr, cm-1): 2080 (νCN), 3098 (νNH).
Anal. Calcd for C42H76B2F8N4OsP4S4: C, 40.3; H, 6.1; N, 4.5.
Found: C, 40.2; H, 6.2; N, 4.4.
Preparation of trans-[OsL2(N2Ph)2] (12). To a solution of 1
(60 mg, 0.071 mmol) in THF (8 mL) was added 4 equiv of
phenylhydrazine hydrochloride (37 mg, 0.28 mmol) and 4 equiv
of Et3N (40 µL, 0.28 mmol). The reaction mixture was stirred at
room temperature overnight, during which the color of solution
turned from orange to brown. The solvent was removed, and the
brown oily solid was washed with hexane and extracted into CH2-
Cl2/Et2O (1:1, v/v). To the filtrate was added hexane, and the
volume was reduced to ca. 5 mL. Cooling at -10 °C afforded
yellowish brown crystals. Yield: 13 mg, 18%. 1H NMR (CDCl3):
δ 1.01 (m, 48H, (CH3)2CH), 1.88 (m, 8H, (CH3)2CH), 7.01-7.45
(m, 10 H, phenyl protons). 31P{1H} NMR (CDCl3): δ 57.81 (s).
(21) Bruker SMART and SAINT+, version 6.02a; Siemens Analytical X-ray
Instruments Inc.: Madison, WI, 1998.
(22) Sheldrick, G. M. SHELXTL-PLUS V.5.1 Software Reference Manual;
Bruker AXS Inc.: Madison, WI, 1997.
5756 Inorganic Chemistry, Vol. 46, No. 14, 2007

Osmium Complexes with a Dithioimidodiphosphinate
Table 1. Crystal Data and Structure Refinement Details for trans-[OsL2(4-tolCN)2] (4), trans-[OsL2(xylNC)2] (6), cis-[Os(L)2(SO2)(H2O)] (cis-8),
trans-[OsL2Cl2] (13), and trans-[OsL2(OMe)2] (14)
param
4
6
cis-8
13
14
empirical formula
fw
C40H70N4OsP4S4
1049.32
C42H74N4OsP4S4
1077.37
C24H58N2O3OsP4S5
897.10
C24H56Cl2N2OsP4S4
885.93
C26H62N2O2OsP4S4
877.10
cryst system
space group
a, Å
b, Å
c, Å
monoclinic
P21/c
9.6387(6)
23.5292(14)
21.6939(13)
triclinic
P1h
monoclinic
P21/c
9.922(6)
14.963(9)
26.216(15)
monoclinic
P21/c
9.6186(8)
15.4228(13)
12.8644(11)
monoclinic
P21/n
9.4626(15)
10.1442(16)
19.756(3)
12.5973(12)
12.7653(12)
17.1029(17)
102.619(2)
98.489(2)
100.346(2)
2589.7(4)
2
R, deg
â, deg
γ, deg
V, Å3
Z
95.5140(10)
94.050(14)
107.589(2)
90.433(3)
4897.2(5)
4
1.423
3883(4)
4
1.535
1819.2(3)
2
1.617
1896.3(5)
2
1.536
F
calcd, g cm-1
temp, K
1.382
250(2)
173(2)
298(2)
100(2)
100(2)
F(000)
2152
2.936
8742/0/478
1.003
0.0597, 0.0881
0.0947, 0.0952
1108
2.778
8955/0/489
0.994
0.0338, 0.0814
0.0433, 0.0852
1824
3.745
6533/0/352
0.983
0.0532, 0.0906
0.1124, 0.1037
896
4.076
4316/0/169
1.033
0.0355, 0.0652
0.0485, 0.0691
896
3.777
3690/0/178
1.026
0.0338, 0.0756
0.0406, 0.0786
µ(Mo KR), cm-1
no. of data/restraints/params
goodness-of-fit on F2
R1,a wR2b (I > 2σ(I))
R1, wR2 (all data)
Table 2. Selected Bond Lengths (Å) and Angles (deg) for trans-[OsL2X2] Compounds
X
param
Os(1)-S(1)
O (1)17
4-tolCN (4)
xylNC (6)
Cl (13)
OMe (14)
2.463(1)
2.457(1)
2.4137(19)
2.424(2)
2.4181(19)
2.431(2)
1.967(6)
1.995(6)
2.026(3)
2.015(3)
2.027(3)
2.007(3)
2.4461(11)
2.4274(13)
2.4383(11)
2.4153(13)
1.955(4)
2.3970(10)
2.3820(10)
2.4153(11)
2.4101(12)
Os(1)-S(2)
Os(1)-S(3)
Os(1)-S(4)
Os(1)-X
1.748(3)
2.3423(9)
1.934(3)
Os(1)-X
1.971(4)
P(1)-S(1)
P(2)-S(2)
P(3)-S(3)
P(4)-S(4)
2.046(1)
2.043(1)
2.0210(16)
2.0234(19)
2.0257(18)
2.0296(18)
2.0511(14)
2.0511(14)
2.0429(15)
2.0403(14)
N(1)/(3)-P(1)
1.593(3)
1.591(5)
1.599(7)
1.589(6)
1.597(7)
1.581(6)
100.54(7)
81.42(7)
98.38(7)
1.582(4)
1.588(4)
1.586(4)
1.591(4)
100.17(4)
80.98(4)
99.31(4)
80.96(4)
170.54(4)
171.49(5)
132.0(3)
128.9(3)
109.38(5)
112.29(6)
110.63(5)
111.46(6)
1.585(3)
1.595(3)
1.598(4)
1.595(4)
N(1)/(3)-P(2)
N(2)/(4)-P(3)
N(2)/(4)-P(4)
S(1)-Os(1)-S(2)
S(2)-Os(1)-S(3)/(1A)
S(3)-Os(1)-S(4)
S(4)-Os(1)-S(1)
S(1)-Os(1)-S(3)/(1A)
S(2)-Os(1)-S(4)
P(1)-N(1)/(3)-P(2)
P(3)-N(2)/(4)-P(4)
Os(1)-S(1)-P(1)
Os(1)-S(2)-P(2)
Os(1)-S(3)-P(3)
Os(1)-S(4)-P(4)
99.8(1)
80.2(1)
100.18(3)
79.82(3)
99.83(4)
80.17(4)
79.70(7)
177.71(7)
178.08(6)
134.3(4)
127.6(3)
130.5(2)
126.9(2)
135.8(4)
116.75(11)
110.40(10)
115.17(11)
109.66(10)
112.14(5)
110.77(5)
109.17(5)
109.82(5)
Results and Discussion
analytically pure sample of compound 2 due to its lipophilic
nature. The 31P{1H} NMR spectrum of a crude sample of
compound 2 in benzene-d6 displays two singlets at δ 58.14
and 58.49 ppm in a ca. 1:1 ratio. It is not clear whether the
sample contained a single Os species with two types of
magnetically inequivalent 31P nuclei or a mixture of two Os
species. Protonation of compound 2 afforded analytically
pure trans-[Os(LH)2(N2)(H2O)][BF4]2 (9) in 80% yield (vide
infra), indicating that compound 2 was predominantly
Syntheses. (A) Os(II) Compounds. The syntheses of
Os-L compounds are summarized in Scheme 1. As reported
previously, treatment of trans-[OsL2(O)2] (1) with hydrazine
hydrate afforded an oily solid 2 that exhibits an νNN peak at
2040 cm-1 in the IR spectrum.17 It may be noted that
reduction of trans-[Os(TPP)(O)2] (TPP ) tetraphenylpor-
phyrin dianion) and trans-[Os(salen)(O)2] (salen ) N,N′-
ethylenebis(salicylideneaminate)) afforded [Os(TPP)(N2)-
(THF)]23 and [Os(salen)(N2)(H2O)],24 the νNN of which were
determined to be 2063 and 2030 cm-1, respectively. There-
fore, compound 2 was tentatively formulated as an Os(II)
dinitrogen compound, possibly “[Os(L)2(N2)(solv)]” (solv )
THF or H2O). We have not been able to obtain a crystalline,
(23) (a) Che, C.-M.; Huang, J.-S.; Li, Z.-Y.; Poon, C.-K.; Tong, W.-F.;
Lai, T.-F.; Cheng, C.-M.; Wang, C.-C.; Wang, Y. Inorg. Chem. 1992,
31, 5220. (b) Li, Z.-Y.; Huang, J.-S.; Chan, M. C.-W.; Cheung, K.-
K.; Che, C.-M. Inorg. Chem. 1997, 36, 3064.
(24) Che, C.-M.; Cheng, W.-K.; Mak, T. C. W. Inorg. Chem. 1986, 25,
703.
Inorganic Chemistry, Vol. 46, No. 14, 2007 5757

Cheung et al.
Scheme 1
Figure 1. Molecular structure of trans-[OsL2(N2Ph)2] (12). The ellipsoids
are drawn at the 30% probability level.
Table 3. Selected Bond Lengths (Å) and Angles (deg) for
cis-[OsL2(SO2)(H2O)] (cis-8)
(HL)2(N2)(H2O)][BF4]2 (9). Despite its 2+ overall charge,
the νNN for dicationic compound 9 (2044 cm-1) is virtually
identical with that in neutral 2. Similarly, protonation of
compounds 3 and 6 with 2 equiv of HBF4 in Et2O gave
cationic trans-[Os(LH)2(PhCN)2][BF4]2 (10) and trans-[Os-
(LH)2(xylNC)2][BF4]2 (11), respectively.
Os(1)-S(1)
2.446(3)
2.426(3)
2.118(3)
1.443(7)
2.033(4)
2.028(4)
93.48(9)
82.23(9)
90.32(9)
82.3(2)
Os(1)-S(2)
2.424(3)
2.399(3)
2.150(7)
1.456(6)
2.017(4)
2.024(4)
100.41(9)
92.96(9)
165.95(8)
83.0(2)
171.3(2)
87.91(9)
96.72(9)
115.90(13)
116.43(13)
136.0(5)
Os(1)-S(3)
Os(1)-S(4)
Os(1)-S(5)
Os(1)-O(1)
O(2)-S(5)
O(3)-S(5)
P(1)-S(1)
P(2)-S(2)
P(3)-S(3)
P(4)-S(4)
(B) Os(IV) Compounds. Reduction of compound 1 with
organohydrazines such as tert-butylhydrazine and 1,1-
diphenylhydrazine resulted in intractable brown materials that
did not crystallize. However, compound 1 reacted with
phenylhydrazine and gave a dark yellow crystalline com-
pound characterized as trans-[OsL2(N2Ph)2] (12). A prelimi-
nary X-ray diffraction study showed that 12 contains two
mutually trans N2Ph- ligands (Figure 1).26 Unfortunately, it
is not possible to analyze the N-N bond distance due to the
disorder found in the N(3) atom in the axial N2Ph- group.
The formulation of 3 as an Os(IV) bis(diazenido) compound
is supported by the observation of an NdN band at 1530
cm-1 in the IR spectrum, which is typical for the diazenido
compounds.27 By comparison, the νNN for trans-[Mo(TPP)-
(N2Ph)2] was observed at 1595 cm-1.28 In addition, no N-H
S(1)-Os(1)-S(2)
S(1)-Os(1)-S(3)
S(1)-Os(1)-S(4)
O(1)-Os(1)-S(1)
O(1)-Os(1)-S(3)
S(5)-Os(1)-S(1)
S(5)-Os(1)-S(3)
O(1)-Os(1)-S(5)
Os(1)-S(2)-P(2)
Os(1)-S(4)-P(4)
P(3)-N(2)-P(4)
S(3)-Os(1)-S(4)
S(2)-Os(1)-S(4)
S(2)-Os(1)-S(3)
O(1)-Os(1)-S(2)
O(1)-Os(1)-S(4)
S(5)-Os(1)-S(2)
S(5)-Os(1)-S(4)
Os(1)-S(1)-P(1)
Os(1)-S(3)-P(3)
P(1)-N1-P(2)
83.2(2)
172.75(9)
94.75(10)
90.8(2)
114.37(13)
111.79(13)
139.0(6)
composed of Os(II) dinitrogen complex(es). Despite its
unknown composition, as-prepared 2 proved to be a useful
starting material for Os-L compounds.
The dinitrogen ligand in compound 2 is labile and can be
readily replaced by σ-donor/π-acid ligands such as nitriles
and isocyanides. Thus, treatment of compound 2 with nitriles
RCN and isonitriles R′NC afforded trans-[OsL2(RCN)2] (R
) Ph (3), 4-tolyl (4), 4-t-BuC6H4 (5)) and trans-[OsL2-
(CNR′)2] (R ) 2,6-dimethylphenyl or xyl (6), t-Bu (7)),
respectively. Compounds 6 and 7 are stable in both the solid
state and in solutions whereas 3-5 are air sensitive in
solutions. Treatment of 2 with SO2(g) afforded [Os(L)2(SO2)-
(H2O)] (8), isolated as an air-sensitive dark brown solid. The
IR spectrum of compound 8 shows the SdO stretch at 1266
cm-1, which is typical for S-bound SO2 ligand. By compari-
son, the νSO for cis-[Ru{N(PPh2S)2}2(PPh3)(SO2)] was
observed at 1286 cm-1.25
1
signal was found in both the H NMR and IR spectra. It
may be noted that cis-[Mo(N2Ph)2(S2CNR2)2] has been
prepared from cis-[Mo(O)2(S2CNR2)2] and phenylhydrazine29
whereas Os mono(diazenido) compounds were generally
synthesized by either reaction of Os carbonyl compounds
with R2N+ or reaction of Os hydride compounds with R2N+
followed by deprotonation with bases such as NaOH.30
(26) Crystal data for compound 12: C66H59N4P5S4Ru; a ) 9.8742(7), b )
10.6299(8), c ) 12.0582(9) Å; R ) 75.7600(10), â ) 70.0860(10), γ
) 79.9050(10)°; V ) 1147.58(15) Å3; triclinic, P1h space group, Z )
1; Fcalcd ) 1.484 g cm-3; T ) 100(2) K; µ ) 3.132 mm-1; no. of data
) 3937; R1 (I > 2σ(I)) ) 0.0346, wR2 (I > 2σ(I)) ) 0.0732, R1 (all
data) ) 0.0362, wR2 (all data) ) 0.0739. N(3) in the N2Ph ligands
was found to be disordered, and the two sites were refined with
occupancies 0.50 and 0.50.
(27) Johnson, B. F. G.; Haymore, B. L.; Dilworth, J. R. In ComprehensiVe
Coordination Chemistry; Wilkinson, G., Gillard, R. D., McCleverty,
J. A., Eds.; Pergamon Press: Oxford, U.K., 1989; Chapter 13.3, p
99.
Attempts to activate the dinitrogen ligand in compound 2
by treatment with electrophiles such as trifluoroacetic
anhydride were unsuccessful. Treatment of compound 2 with
HBF4 in Et2O resulted in protonation of the L- ligands and
the formation of highly air-sensitive dicationic trans-[Os-
(28) Colin, J.; Bulter, G.; Weiss, R. Inorg. Chem. 1980, 19, 3828.
(29) Bishop, M. W.; Bulter, G.; Chatt, J.; Dilworth, J. R.; Leigh, G. J. J.
Chem. Soc., Dalton Trans. 1979, 1843.
(25) Leung, W.-H.; Zheng, H.; Chim, J. L. C.; Chan, J.; Wong, W.-T.;
Williams, I. D. J. Chem. Soc., Dalton Trans. 2000, 423.
5758 Inorganic Chemistry, Vol. 46, No. 14, 2007

Osmium Complexes with a Dithioimidodiphosphinate
Scheme 2
Reduction of 1 with SnCl2 in THF gave the dichloride
compound trans-[Os(L)2Cl2] (13). It may be noted that trans-
[Os(TPP)Cl2] has been prepared by reduction of trans-[Os-
(TPP)(O)2] with SnCl2.31 Compound 13 is remarkably
substitutionally inert. No substitution was found when 13
was reacted with nucleophiles such as azide, alkoxides,
amides, and cyanide. An attempt to abstract the chlorides in
13 by treatment with silver triflate failed.
The Os(IV) bis(diazenido) compound 12 is diamagnetic
whereas the dichloride compound 13 is paramagnetic with
measured µeff of 1.8 µB which is similar to that for trans-
[Os(TPP)Cl2] (1.63 µB).31 The diamagnetic behavior of
compound 12 is consistent with the (dxy)2(dxz)2 or (dxy)2(dyz)2
ground electron configuration that has been found for
bis(amido)osmium(IV) porphyrins, e.g., trans-[Os(TPP)-
(NHPh)2].23b The splitting of the (dyz, dzx) set for trans-
[M(TPP)(NPh2)2] (M ) Ru, Os) has been explained in terms
to the π interaction between the pπ orbital of the coplanar
amido ligands and one of the metal dπ orbitals.32 By contrast,
the dialkoxyosmium(IV) porphyrins trans-[Os(TPP)(OR)2],
in which the alkoxy ligands act as pseudo double-faced π
donors, are paramagnetic with the triplet (dxy)2(dyz)1(dzx)1
ground state.23a
Air Oxidation of Compound 2. Previously, we reported
that oxidation of compound 2 in Et2O in air gave the
dioxoosmium(VI) compound 1.17 However, when the oxida-
tion of compound 2 was carried out in MeOH/hexane, orange
crystals characterized as the Os(IV) dimethoxy compound
trans-[OsL2(OMe)2] (14) were isolated. The measured µeff
of 1.6 µB for compound 14 is similar to that of trans-[Os-
(salen)(OMe)2] (1.33 µB)24 but smaller than that of trans-
[Os(TPP)(OMe)2] (2.27 µB).23a Oxidation of compound 2 in
ROH/hexane (R ) Et, i-Pr) also gave red solutions, indicative
of formation of the Os(IV) alkoxy species. Unfortunately,
we were not able to crystallize these dialkoxy compounds
due to their high solubility in organic solvents. It may be
noted that trans-[Os(TPP)(OR)2] (R ) Me, Et, PhCH2) have
been synthesized from oxidation of [Os(TPP)(N2)(THF)] in
ROH/CH2Cl2 in air.23a Although compound 14 is stable in
CH2Cl2/MeOH solution, it is readily oxidized in air to the
dioxo compound 1 in CH2Cl2 solution. This is in contrast
with trans-[Os(TPP)(OMe)2]23a and trans-[Os(salen)(OMe)2]24
Figure 2. Optical spectral change for the air oxidation of trans-[OsL2-
(OMe)2] in CH2Cl2 solution (time interval ) 2 min).
that are air stable in CH2Cl2 solutions. It seems likely that,
in CH2Cl2 solution and in the absence of MeOH, compound
14 is in equilibrium with an Os(IV) dihydroxy or monooxo
aquo species that can be readily air oxidized to compound
1, possibly via an Os peroxo species. MeOH probably
suppresses the exchange of the methoxy ligands in compound
14 with OH-/H2O, thus inhibiting its air oxidation (Scheme
2). Figure 2 shows the optical spectral trace for the oxidation
of compound 14 in CH2Cl2 in air. The observation of
isosbestic points at 285, 355, and 508 nm indicates that the
air oxidation of compound 14 is a clean process and no
intermediate(s) had accumulated during the oxidation.
NMR Spectroscopy. Compounds 3-7 exhibit a single 31P
resonance at ca. δ 58 ppm, which is very close to that of
compound 1 (δ 60.7 ppm), indicative of the trans geometry
of these Os(II) compounds. The 31P{1H} NMR spectrum of
a recrystallized sample of compound 8, which has been
identified as cis-[OsL2(SO2)(H2O)] by an X-ray diffraction
study (vide infra), in C6D6 shows an intense singlet at δ 59.49
ppm characteristic of trans-Os(L)2-type compounds along
with four resonances at δ 61.30 (d), 59.37 (br s), 59.16 (br
s), and 56.40 (d) ppm attributable to cis-8. This result
suggests that while compound 8 prefers to crystallize in the
trans form in the solid state, cis-8 readily isomerizes to the
trans isomer in C6D6. Similar cis-trans isomerization has
been observed for [RuL2(PPh3)X]-type compounds previ-
ously. For example, [Ru{N(Ph2PS)2}2(PPh3)(py)] (py )
pyridine) in CDCl3 was found to contain a ca. 3:2 mixture
of the cis and trans forms.25 For compounds 10 and 11, the
31P resonances occur at more upfield positions (δ 89.38 and
89.90 ppm) than those of Os(II)-L compounds but are simi-
lar to that for free HL (δ 91.2 ppm). In addition, broad sing-
lets assignable to the NH protons at δ 6.30 and 6.36 ppm,
1
respectively, were observed in their H NMR spectra. The
NMR data confirmed that the nitrogen atom in L- was pro-
tonated upon treatment of compounds 10 and 11 with HBF4.
For the bis(phenyldiazenido) compound 12, the resonances
for the isopropyl protons occur at the normal diamagnetic
region (δ 1.01 and 1.88 ppm). The 31P{1H} NMR spectrum
displays a singlet at δ 57.81 ppm, consistent with its solid-
state structure. Although compounds 13 and 14 are para-
(30) (a) Haymore, B. L.; Ibers, J. A. Inorg. Chem. 1975, 14, 2784. (b)
Albertin, G.; Antoniutti, S.; Bordignon, E. J. Chem. Soc., Dalton Trans.
1989, 2353.
(31) Smieja, J. A.; Omberg, K. M.; Busuego, L. N.; Breneman, G. L.
Polyhedron 1994, 13, 339.
(32) (a) Huang, J.-S.; Che, C.-M.; Li, Z.-Y.; Poon, C.-K. Inorg. Chem.
1992, 31, 1313. (b) Yang, S.-Y.; Leung, W.-H.; Lin, Z. Organome-
tallics 2001, 20, 3198.
1
magnetic, they exhibit well-resolved H NMR signals that
are downfield shifted compared with diamagnetic Os-L
compounds (e.g., the resonances for the Me2CH protons
Inorganic Chemistry, Vol. 46, No. 14, 2007 5759

Cheung et al.
Figure 3. Molecular structure of trans-[OsL2(4-tolCN)2] (4). The ellipsoids
are drawn at the 30% probability level.
Figure 5. Molecular structure of cis-[OsL2(SO2)(H2O)] (cis-8). The
ellipsoids are drawn at the 30% probability level.
Figure 6. Molecular structure of trans-[OsL2Cl2] (13). The ellipsoids are
drawn at the 30% probability level.
Figure 4. Molecular structure of trans-[OsL2(xylNC)2] (6). The ellipsoids
are drawn at the 30% probability level.
occur at δ 3.84 and 3.40 and 3.64 ppm, respectively; cf. δ
2.51 ppm for compound 1). The axial methoxy protons in
compound 14 appears as a singlet at δ 42.90 ppm (cf. δ
34.23 for trans-[Os(TPP)(OMe)2]23a). The 31P{1H} NMR
spectrum of 14 shows a singlet at δ 34.65 ppm whereas no
31P resonant signals were observed for 13.
Crystal Structures. The molecular structures of com-
pounds 4, 6, cis-8, 13, and 14 are shown in Figures 3-7,
respectively. Selected bond lengths and angle for compounds
4, 6, 13, and 14 are compiled in Table 2, and those of cis-8,
in Table 3. The geometry around Os in compounds 4, 6, 13,
and 14 is pseudooctahedral with the two L- ligands on the
equatorial planes. The Os-SPNP′S′ rings in these complexes
are nonplanar with boatlike confirmation. The P-S distances
(2.026(2)-2.049(2) Å) are longer than those in the free
ligand HL (1.941(1) and 1.949(1) Å)18 whereas the P-N
distances (1.586(5)-1.594(4) Å) are shorter than those in
the latter (1.682(3) and 1.684(2) Å).18 The Os-S distances
for the Os(IV) compounds are similar to those of the Os(II)
compounds. It is worth noting that the Os-S distances in
the Os(II) compound 4 (2.414(2)-2.431(2) Å) are slightly
Figure 7. Molecular structure of trans-[OsL2(OMe)2] (14). The ellipsoids
are drawn at the 30% probability level.
shorter than those in the dioxoosmium(VI) compound 1
(average 2.460 Å).17 This result probably reflects strong
Os-S interactions in the Os(II)-L compound. The Os-N
distances in compound 4 (1.967(6) and 1.995(6) Å) and the
Os-C distances in compound 6 [1.955(4) and 1.971(4) Å]
are similar to those of related compounds, e.g., 2.081(8)-
2.097(8) Å for fac-[Os(PMe2Ph)3(MeCN)3]2+ 33 and 2.00(3)
Å for trans-[OsBr2(CN-t-Bu)4].34 The Os-Cl distance in
5760 Inorganic Chemistry, Vol. 46, No. 14, 2007

Osmium Complexes with a Dithioimidodiphosphinate
Table 4. Formal Potentials (E1/2)a for Os-L Complexes
Scheme 3
E
1/2/V vs Cp2Fe+/0
Os(V/IV) Os(IV/III) Os(III/II)
complex
trans-[OsL2(PhCN)2] (4)
0.64
0.62
-0.63
-0.67
-0.68
trans-[OsL2(4-tolCN)2] (5)
trans-[OsL2(4-t-BuC6H4CN)2] (6)
trans-[OsL2(xylNC)2] (7)
trans-[Os(HL)2(PhCN)2][BF4]2 (11)
trans-[OsL2Cl2] (13)
0.64
0.12b
0.93
0.33
-0.62
trans-[OsL2(OMe)2] (14)
0.31b
a Potentials measured at a glassy carbon electrode in CH2Cl2 solutions
that of trans-[Os(Busalch)Cl2] (Busalch ) bis(3,5-di-tert-
butylsalicylidene)-1,2-cyclohexanediamine) (-0.77 V).37 The
CV of the dimethoxy compound 14 displays an irreversible
oxidation wave with Epa ) 0.12 V, which is tentatively
assigned to the Os(IV/V) oxidation. By contrast, the Os(V/
IV) couples for trans-[Os(TPP)(OMe)2]38 and trans-[Os-
(salen)(OMe)2]39 observed at 0.37 and 0.50 V, respectively,
are reversible.
with 0.1 M [n-Bu4N][PF6] as supporting electrolyte; scan rate ) 100 mV
s-1 b Irreversible, Epa value.
.
compound 13 (2.3423(9) Å) and the Os-O distance in
compound 14 (1.934(3) Å) compare well with those of the
porphyrin compounds trans-[Os(TPP)(OEt)2] (1.915(4) Å)23a
and trans-[Os(TPP)Cl2] (2.294(2) Å).31 The relatively short
Os-O distance (cf. ca. 2.1 Å for normal Os-O single bonds)
and large Os-O-C angle (127.9(3)°) in 14 are indicative
of dπ(Os)-pπ(O) interaction.
The geometry about Os in cis-8 is pseudooctahedral with
the SO2 and H2O ligands cis to each other. The Os-S(trans
to SO2) distance (2.446(3) Å) is longer than the other Os-S
distances (2.399(3)-2.426(3) Å) due to the trans influence
of the SO2 ligand. The Os-SO2 distance of 2.118(3) Å is
shorter than that in [Os(H)(SO2)Cl(CO){P(C6H11)3}2] (2.239-
(3) Å)35 that has a trans-directing hydride ligand opposite to
the SO2 ligand. The Os-OH2 distance of 2.150(7) Å is
normal.
Electrochemistry. Formal potentials of Os-L complexes
have been determined by cyclic voltammetry, and the results
are summarized in Table 4. The cyclic voltammogram (CV)
for compound 3 in CH2Cl2 shows two reversible couples at
-0.63 and 0.64 V vs Cp2Fe+/0, which are assigned as the
metal-centered Os(III/II) and Os(IV/III) couples, respectively.
Similar Os(III/II) (-0.67 and -0.68 V, respectively) and Os-
(IV/III) (0.62 and 0.64 V, respectively) potentials were found
for the bis(nitrile) compounds 4 and 5. Unlike compounds
3-5, the oxidation of the bis(isonitrile) complex 6 is
irreversible (Epa ) 0.12 V). As one might expect, upon
protonation the Os(III/II) and Os(IV/III) potentials for
compound 3 were shifted to more anodic positions (0.33 and
0.93 V, respectively, for compound 10). However, the anodic
shift in the Os(III/II) potential (∆E1/2 ) 0.9 V) is more
1-Catalyzed Aerobic Oxidation of PPh3. Treatment of
compound 1 with excess PPh3 (ca. 4 equiv) led to formation
of an intractable paramagnetic material that did not crystal-
lize. 31P NMR spectroscopy indicated that ca. 1 equiv of
Ph3PO was produced, suggesting that the paramagnetic
species is an Os(IV) compound. On the other hand, reaction
of compound 1 with more basic phosphines led to formation
of diamagnetic Os(II) phosphine compounds. For example,
treatment of 1 with 4 equiv of PMePh2 afforded air-sensitive
cis-[OsL2(PMePh2)2] (15). The 31P{1H} NMR spectrum of
15 displays three multiplets at δ -42.61, 49.16, and 50.10
ppm, consistent with the cis geometry of the compound. The
facts that compound 1 can be reduced to an Os(IV) species
by PPh3 and that the Os(IV) compound 14 is readily air
oxidized to give compound 1 suggest that catalytic oxidation
of PPh3 with compound 1 using oxygen as terminal oxidant
is feasible. Indeed, stirring a solution of PPh3 in chloroform
at room temperature under 1 atm pressure of oxygen in the
presence of 10 mol % of compound 1 gave Ph3PO in 92%
yield in 2 d. The dimethoxy compound 14 can also catalyze
aerobic oxidation of PPh3 with a similar efficiency (96%,
42 h). It seems likely that the catalytic cycle for the aerobic
oxidation of PPh3 involves the interconversion between
compound 1 and an Os(IV) intermediate (Scheme 3). The
catalytic activity of compound 1 is rather low compared with
other metal-oxo catalysts, e.g., cis-[Mo(O)2(S2CNEt2)2]40
and [Ir(mes)3(O)], where mes ) 2,4,6-trimethylphenyl,41
presumably due to the strong binding of PPh3 or OPPh3 to
the Os center that inhibits the air oxidation of Os(IV) to Os-
(VI). Additional experimental work is needed to elucidate
the mechanism of the Os-catalyzed aerobic oxidation of PPh3.
significant than that for the Os(IV/III) potential (∆E1/2
)
0.31 V). This is probably due to the fact that the stability of
the Os(II) state is more affected by the cationic charge
(through weakening of Os-to-nitrile back-bonding) compared
with that for the Os(III) and Os(IV) states.
The CV of the dichloride compound 13 exhibits a
reversible couple at -0.62 V that is assigned as the Os(IV/
III) couple. The Os(IV/III) potential for compound 13 is more
negative than that of trans-[Os(TTP)Cl2] (TTP ) tetrakis-
(p-tolyl)porphyrin dianion) (-0.33 V)36 but less positive than
(36) Leung, W.-H.; Hun, T. S. M.; Wong, K.-Y.; Wong, W.-T. J. Chem.
Soc., Dalton Trans. 1994, 2713.
(37) Zhang, J.; Liang, J.-L.; Sun, X.-R.; Zhou, H.-B.; Zhu, N.-Y.; Zhou,
Z.-Y.; Chan, P. W. H.; Che, C.-M. Inorg. Chem. 2005, 44, 3942.
(38) Che, C.-M.; Leung, W.-H.; Chung, W.-C. Inorg. Chem. 1990, 29, 1841.
(39) Cheng, W.-K.; Wong, K.-Y.; Tong, W.-F.; Lai, T.-F.; Che, C.-M. J.
Chem. Soc., Dalton Trans. 1992, 91.
(33) Bruno, J. W.; Huffman, J. C.; Caulton, K. G. J. Am. Chem. Soc. 1984,
106, 1663.
(34) Jones, R. A.; Whittlesey, B. R.; Atwood, J. L.; Hunter, W. E.
Polyhedron 1984, 3, 385.
(40) Barral, R.; Bocard, C.; de Roch, I. S.; Sajus, L. Tetrahedron Lett.
1972, 13, 1693.
(41) Jacobi, B. G.; Laitar, D. S.; Pu, L.; Wargocki, M. F.; DiPasquale, A.
G.; Fortner, K. C.; Schuck, S. M.; Brown, S. N. Inorg. Chem. 2002,
41, 4815.
(35) Ryan, R. R.; Kubas, G. J. Inorg. Chem. 1978, 17, 637.
Inorganic Chemistry, Vol. 46, No. 14, 2007 5761

Cheung et al.
Concluding Remarks
may anticipate that OsL2 compounds may find applications
in atom/group transfer reactions. Unlike the porphyrin and
salen analogues, trans-[OsL2(OMe)2] is air sensitive in CH2-
Cl2 solution and easily oxidized in air to dioxoosmium(VI)
species. 1 can catalyze aerobic oxidation of PPh3, and the
catalytic cycle is believed to involve an interconversion
between 1 and an Os(IV) intermediate.
We found that the dinitrogen compound 2 prepared by
reduction of trans-[OsL2(O)2] (1) with hydrazine hydrate is
a useful starting material for Os-L compounds. Substitution
of 2 with Lewis bases L′ such as nitriles and isonitriles
afforded trans-[OsL2L′2] whereas air oxidation of compound
2 in MeOH/hexane gave trans-[OsL2(OMe)2]. Reduction of
1 with phenylhydrazine and SnCl2 afforded trans-[OsL2(N2-
Ph)2] and trans-[OsL2Cl2], respectively. It appears that there
is a close resemblance in chemistry between the OsS4 core
in the Os-L compounds and the OsN4 and OsN2O2 cores in
related porphyrin and Schiff base compounds, e.g., the OsVI-
(O)2 T OsIVX2 T OsIIL2 interconversion. On the basis of
the Os(IV/III) formal potential of [OsIV(chelate)Cl2], the
Acknowledgment. We thank Dr. Herman H. Y. Sung
for solving the crystal structures. The financial support
from the Hong Kong Research Grants Council (Project
No. 602104) is gratefully acknowledged. Q.-F.Z. thanks
the Science and Technological Fund of Anhui Province,
P. R. China, for the Outstanding Youth Award (Grant
06046100). We thank the reviewers for useful suggestion
and comments.
donor strength of chelate is ranked in the order salen2-
>
(L-)2 > TPP2-. A similar trend was obtained considering
the IR N-N stretching frequencies for [Os(chelate)(N2)-
(solv)]. Given the reported catalytic activity of Os salen37
and porphyrin42 compounds in organic transformations, one
Supporting Information Available: Tables of crystal data, final
atomic coordinates, anisotropic thermal parameters, and complete
bond lengths and angles for compounds 4, 6, cis-8, 13, and 14.
This material is available free of charge via the Internet at
http://pubs.acs.org.
(42) (a) Smith, D. A.; Reynolds, D. N.; Woo, L. K. J. Am. Chem. Soc.
1993, 115, 2511. (b) Che, C. M.; Huang, J.-S. Coord. Chem. ReV.
2002, 231, 151.
IC070048E
5762 Inorganic Chemistry, Vol. 46, No. 14, 2007