Ruthenium complexes with dithiophosphonates [Ar(RO)PS2] - and [Fc(RO)PS2]- (Ar = p -CH 3OC6H4, Fc = Fe(η5-C 5H4)(η5-C5H5))

Article abstract of DOI:10.1021/om100209k

Treatment of dimeric [(η⁶-p-cymene)RuCl(μ-Cl)] ₂ with Lawessons reagent [ArP(S)(μ-S)]₂ (Ar = p-C ₆H₄OMe) in THF gave [(η⁶-p-cymene)Ru{μ- η¹(S), η²(S,S′)-ArP(S)S₂}] ₂ (1) as the sole isolable product. The chlorides in the starting ruthenium compound were substituted by [ArP(S)S₂]^2- as a bridging dithiolato ligand. Interactions of [Ru(PPh₃) ₃Cl₂] and [RuHCl(CO)(PPh₃)₃] with Lawessons reagent in the presence of ammonium hydroxide gave the dinuclear neutral complexes [Ru(μ- η¹(O), η¹(S), η¹(S,S′)-ArPOS₂)(PPh₃) ₂]₂ (2) and [Ru(CO)(μ- η¹(O), η²(S,S′)-ArPOS₂)(PPh₃)]₂ (3), respectively, in which the [ArPOS₂]^2- ligands bind the two Ru atoms via both sulfur and oxygen atoms. Reaction of dimeric [Cp*Ru(OMe)]₂ (Cp* = η⁵-C ₅Me₅) with Lawessons reagent in the presence of ammonium hydroxide led to isolation of a novel ruthenium(IV) complex, [Cp*Ru{(ArPS₂O)₂H}] (4). Reaction of [Ru(PPh ₃)₃Cl₂] or [RuHCl(CO)(PPh₃) ₃] with Na[FcP(OMe)S₂], which was prepared from [FcP(S)(μ-S)]₂ (Fc = Fe(η⁵-C₅H ₄)(η⁵-C₅H₅)) and MeONa in methanol, gave the neutral mononulcear complexes cis-[Ru{Fc(OCH ₃)PS₂}₂(L′)(PPh₃)] (L′ = PPh₃ 5, CO 6). Interaction of [Ru(PPh₃) ₃Cl₂] or [RuHCl(CO)(PPh₃)₃] with [FcP(S)(μ-S)]₂ in the presence of ammonium hydroxide in THF gave [Ru{Fc(OH)PS₂}₂(L′)(PPh₃)] (L′ = PPh₃ 7, CO 8). Treatment of [(η⁶-p-cymene)RuCl(μ- Cl)]₂ with [FcP(OH)S(SH)] in the presence of excess NaHCO₃ led to isolation of [(η⁶-p-cymene)Ru{η¹(S), η²(S,S′)-FcPS₂OP(S)SFc}] (9). The crystal structures of 1, 2, 3·CH₂Cl₂·THF, 4·CH₂Cl₂·0.5H₂O, 6, 7·CH₂Cl₂·³/₄C ₆H₁₄, and 9·CH₂Cl₂ along with their spectroscopic properties are reported.

Full text of DOI:10.1021/om100209k

2752 Organometallics 2010, 29, 2752–2760
DOI: 10.1021/om100209k
Ruthenium Complexes with Dithiophosphonates [Ar(RO)PS2]- and
[Fc(RO)PS2]- (Ar = p-CH3OC6H4, Fc = Fe(η5-C5H4)(η5-C5H5))
Xi-Ying Wang, Yan Li, Qing Ma, and Qian-Feng Zhang*
Institute of Molecular Engineering and Applied Chemistry, Anhui University of Technology, Ma’anshan,
Anhui 243002, People’s Republic of China
Received March 18, 2010
Treatment of dimeric [(η6-p-cymene)RuCl(μ-Cl)]2 with Lawesson’s reagent [ArP(S)(μ-S)]2 (Ar =
p-C6H4OMe) in THF gave [(η6-p-cymene)Ru{μ-η1(S),η2(S,S0)-ArP(S)S2}]2 (1) as the sole isolable
product. The chlorides in the starting ruthenium compound were substituted by [ArP(S)S2]2- as a
bridging dithiolato ligand. Interactions of [Ru(PPh3)3Cl2] and [RuHCl(CO)(PPh3)3] with Lawesson’s
reagent in the presence of ammonium hydroxide gave the dinuclear neutral complexes [Ru(μ-η1-
(O),η1(S),η1(S,S0)-ArPOS2)(PPh3)2]2 (2) and [Ru(CO)(μ-η1(O),η2(S,S0)-ArPOS2)(PPh3)]2 (3), respec-
tively, in which the [ArPOS2]2- ligands bind the two Ru atoms via both sulfur and oxygen atoms.
Reaction of dimeric [Cp*Ru(OMe)]2 (Cp*=η5-C5Me5) with Lawesson’s reagent in the presence of
ammonium hydroxide led to isolation of a novel ruthenium(IV) complex, [Cp*Ru{(ArPS2O)2H}] (4).
Reaction of [Ru(PPh3)3Cl2] or [RuHCl(CO)(PPh3)3] with Na[FcP(OMe)S2], which was prepared
from [FcP(S)(μ-S)]2 (Fc=Fe(η5-C5H4)(η5-C5H5)) and MeONa in methanol, gave the neutral
mononulcear complexes cis-[Ru{Fc(OCH3)PS2}2(L0)(PPh3)] (L0 = PPh3 5, CO 6). Interaction of
[Ru(PPh3)3Cl2] or [RuHCl(CO)(PPh3)3] with [FcP(S)(μ-S)]2 in the presence of ammonium hydroxide
in THF gave [Ru{Fc(OH)PS2}2(L0)(PPh3)] (L0 = PPh3 7, CO 8). Treatment of [(η6-p-cymene)-
RuCl(μ-Cl)]2 with [FcP(OH)S(SH)] in the presence of excess NaHCO3 led to isolation of [(η6-
p-cymene)Ru{η1(S),η2(S,S0)-FcPS2OP(S)SFc}] (9). The crystal structures of 1, 2, 3 CH2Cl2 THF,
3
3
4 CH2Cl2 0.5H2O, 6, 7 CH2Cl2 3/4C6H14, and 9 CH2Cl2 along with their spectroscopic properties
are reported.
3
3
3
3
3
Introduction
date;5-9 however, the corresponding chemistry of dithiopho-
sphate and dithiophosphonate has not been well developed.9,10
Indeed, thiophosphorus species are an important class of
sulfur-donor ligands.11 For example, the notable Lawesson’s
dimer [(p-C6H4OMe)P(S)(μ-S)]2 can undergo a ring-opening
reaction by nucleophilic attack under suitable conditions,
resulting in formation of the typical dithiophosphate and
dithiophosphonate ligands.12-14 Even though the synthesis
and characterization of thiophosphorus ligands [(RO)2PS2]-
and [(RO)RPS2]- of a few transition metal derivatives have
been investigated in depth,11-18 very little is known about the
chemistry of ruthenium-dithiophosphonate and -dithiopho-
sphonate complexes.9,10 Similarly, although the coordinative
Ruthenium-sulfur complexes with sulfur-donor ligands
are well known for their industrial applications in hydro-
desulfurization (HDS) and related processes,1,2 partly because
of the high catalytic activity of RuS2 in various hydrogena-
tion processes.3,4 The chemistry of ruthenium complexes
with dithioacid-based ligands such as dithiocarbamate and
dithiocarbonate has been the subject of continuous study to
*To whom correspondence should be addressed. E-mail: zhangqf@
ahut.edu.cn.
(1) Stiefel, E. I.; Matsumoto, K., Eds. Transition Metal Sulfur
Chemistry; ACS Symposium Series 653; American Chemical Society:
Washington, DC, 1996; pp 216-307, and references therein.
(2) Vit, Z.; Zdrazil, M. J. Catal. 1989, 119, 1–7.
(3) Chianelli, R. R.; Daage, M.; Ledoux, M. J. Adv. Catal. 1994, 40,
177–232.
(10) Liu, X.; Zhang, Q. F.; Leung, W. H. J. Coord. Chem. 2005, 58,
1299–1305.
(11) Haiduc, I. J. Organomet. Chem. 2001, 623, 29–42.
(12) Bhattacharyya, P.; Slawin, A. M. Z.; Woollins, J. D. Chem.;
Eur. J. 2002, 8, 2705–2711.
(4) Hidai, M.; Kuwata, S.; Mizobe, Y. Acc. Chem. Res. 2000, 33,
46–52.
(5) Leung, W. H.; Chim, J. L. C.; Hou, H.; Hun, T. S. M.; Williams,
I. D.; Wong, W. T. Inorg. Chem. 1997, 36, 4432–4437.
(6) Ng, S.; Ziller, J. W.; Farmer, P. J. Inorg. Chem. 2004, 43, 8301–
8309.
(7) Noda, K.; Ohuchi, Y.; Hashimoto, A.; Fujiki, M.; Itoh, S.;
Iwatsuki, S.; Noda, T.; Suzuki, T.; Kashiwabara, K.; Takagi, H. D.
Inorg. Chem. 2006, 45, 1349–1355.
(8) Wu, F.H.;Duan, T.;Lu, L;Zhang, Q. F.;Leung, W.H.J. Organomet.
Chem. 2009, 694, 3844–3851.
(9) Tay, E. P. L.; Kuan, S. L.; Leong, W. K.; Goh, L. Y. Inorg. Chem.
2007, 46, 1440–1450.
(13) Gray, I. P.; Slawin, A. M. Z.; Woollins, J. D. Dalton Trans. 2004,
2477–2486.
(14) Shi, W.; Shafaei-Fallah, M.; Anson, C. E.; Rothenberger, A.
Dalton Trans. 2006, 3257–3262.
(15) Shi, W.; Shafaei-Fallah, M.; Anson, C. E.; Rothenberger, A.
Dalton Trans. 2005, 3909–3912.
(16) Haiduc, I.; Mezei, G.; Micu-Semeniuc, R.; Edelmann, F. T.;
Fischer, A. Z. Anorg. Allg. Chem. 2006, 632, 295–300.
(17) Van, Z.; Werner, E. Comments Inorg. Chem. 2010, 31, 13–45.
(18) Weng, Z.; Leong, W. K.; Vittal, J. J.; Goh, L. Y. Organometallics
2003, 22, 1645–1656.
r
pubs.acs.org/Organometallics
Published on Web 05/26/2010
2010 American Chemical Society

Article
Organometallics, Vol. 29, No. 12, 2010 2753
behavior of ferrocenyl-dithiophosphonate [FcP(OR)S2]- (R=
Me, Et, i-Pr, and CH2C6H4N3, Fc=Fe(η5-C5H4)(η5-C5H5))
with transition metals was recently studied by Woollins and
Elemental analyses were carried out using a Perkin-Elmer 2400
CHN analyzer.
Preparation of [(η6-p-cymene)Ru{μ-η1(S),η2(S,S0)-ArP(S)S2}]2
(1). To a solution of Lawesson’s reagent (82 mg, 0.20 mmol) in
THF (10 mL) was added a solution of [(η6-p-cymene)RuCl-
(μ-Cl)]2 (122 mg, 0.20 mmol) in THF (10 mL). The mixture was
heated at reflux for 1 h. The solvent was removed in vacuo, and the
residue was recrystallized from CH2Cl2/hexane to give orange
crystalline solids in two days at room temperature. Yield: 113 mg,
Suss-Fink et al.,19-22 no ruthenium complex with ferrocenyl-
€
phosphonodithiolate as a dithio ligand has been reported
to date.
Recently, Woollins and co-workers successfully developed
a series of metal complexes with the bidentate chelating
ligands [N(R2PQ)2]- (Q=O, S, Se; R=alkyl or phenyl), which
exhibit interesting stereochemistry.23 We studied the coordina-
tively unsaturated ruthenium-sulfur complexes Ru[N(R2PS)2]2-
(PPh3) (R=Ph, i-Pr), which are capable of activating H2, SO2,
and hydrazine.24,25 Five-coordinate ruthenium-sulfur carbene
complexes Ru[N(R2PS)2]2(dCHPh) were found to be active
catalysts for the ring-opening polymerization of norbornene.26
As part of our ongoing studies of ruthenium-sulfur complexes,
we are interested in the coordination properties of phosphorus-
1,1-dithiolates as a general class of ligands toward ruthenium.
The versatile bonding and structural features as well as fascinat-
ing chemical and electrochemical reactivities of ruthenium 1,1-
dithiolates complexes have prompted us to make a systematic
study of ruthenium dithiophosphonate complexes.8 The synthesis
and crystal structures of ruthenium-dithiophosphonate com-
plexes, obtained from the a series of reactions of ruthenium com-
pounds such as [Ru(PPh3)3Cl2], [RuHCl(CO)(PPh3)3], [(η6-
p-cymene)RuCl(μ-Cl)]2, and [Cp*Ru(OMe)]2 (Cp*=η5-C5Me5)
with dithiophosphonates [Ar(RO)PS2]- and [Fc(RO)PS2]-
(Ar = p-CH3OC6H4, Fc = Fe(η5-C5H4)(η5-C5H5)), respec-
tively, will be reported in this paper.
1
0.12 mmol, 56% (based on Ru). H NMR (300 MHz, CDCl3):
δ (ppm) 1.34 (d, 6H, CH(CH3)2), 2.15 (s, 3H, PhCH3), 3.04
(septet, 1H, CH(CH3)2), 3.74 (s, 6H, OCH3), 5.40 and 5.68 (dd,
4H, J=8.2 Hz, aryl H incymene), 6.79 (d, 4H, J=7.6 Hz, aryl H),
7.72-7.90 (dd, 4H, J = 7.7 Hz, aryl H). 31P{1H} NMR (121.5
MHz, CDCl3): δ (ppm) 84.2 (s) ppm. Selected IR (KBr, cm-1):
1582 (s), 1432 (s), 1246 (s), 685 (s), 558 (s), 534 (m), 501 (s). MS
(FAB): m/z 939 [Mþ], 468 [1/2Mþ - 1]. Anal. Calcd for C34H42-
O2P2S6Ru2: C, 43.5; H, 4.51. Found: C, 43.3; H, 4.47.
Preparation of [Ru(μ-η1(O),η1(S),η1(S,S0)-ArPOS2)(PPh3)2]2
(2). To a slurry of Lawesson’s reagent (41 mg, 0.10 mmol) and
17% NH3 H2O (0.2 mL) in THF (10 mL) was added a solution
3
of [Ru(PPh3)3Cl2] (192 mg, 0.20 mmol) in THF (10 mL). The
mixture was stirred at room temperature for 6 h. The solvent was
removed in vacuo, and the residue was recrystallized from
CH2Cl2/hexane to give orange crystalline solids in three days
at room temperature. Yield: 95 mg, 0.06 mmol, 56% (based on
Ru). 1H NMR (300 MHz, CDCl3): δ (ppm) 3.74 (s, 6H, OCH3),
6.71 (d, 4H, J = 7.6 Hz, aryl H), 7.24-7.47 (m, 60H, PPh3),
7.82-8.04 (dd, 4H, J = 7.6 Hz, aryl H). 31P{1H} NMR (121.5
MHz, CDCl3): δ (ppm) 36.9 (s, 4P, PPh3), 59.3 (s, 2P, ArPS2O).
Selected IR (KBr, cm-1): 1587 (s), 1431 (s), 1245 (s), 1022 (s), 676
(s), 558 (s), 533 (m), 499 (s). MS (FAB): m/z 1688 [Mþ], 843
[1/2Mþ - 1]. Anal. Calcd for C86H74O4P6S4Ru2: C, 61.2; H,
4.42. Found: C, 61.1; H, 4.40.
Experimental Section
Preparation of [Ru(CO)(μ-η1(O),η2(S,S0)-ArPOS2)(PPh3)2]2
3
General Considerations. All synthetic manipulations were
carried out under dry nitrogen by standard Schlenk techniques.
Solvents were purified, distilled, and degassed prior to use.
Lawesson’s reagent, [ArP(S)(μ-S)]2 (Ar = p-CH3OC6H4), was
purchased from Aldrich and used without further purification.
[FcP(S)(μ-S)]2,19 [Ru(PPh3)3Cl2],27 [RuHCl(CO)(PPh3)3],28 [(η6-
CH2Cl2 THF (3 CH2Cl2 THF). To a slurry of Lawesson’s
reagent (41 mg, 0.10 mmol) and 17% NH3 H2O (0.2 mL) in
3
3
3
3
THF (10 mL) was added a solution of [RuHCl(CO)(PPh3)3]
(190 mg, 0.20 mmol) in THF (10 mL). The mixture was heated at
reflux for 4 h. The solvent was removed in vacuo, and the residue
was recrystallized from CH2Cl2/THF/hexane to give orange
crystalline solids in a week at room temperature. Yield: 89 mg,
0.05 mmol, 47% (based on Ru). 1H NMR (300 MHz, CDCl3):
δ (ppm) 2.52 (s, 4H, THF), 3.62 (s, 4H, THF), 3.76 (s, 6H,
OCH3), 5.32 (s, 2H, CH2Cl2), 6.75 (d, 4H, J =7.8 Hz, aryl H),
7.23-7.45 (m, 60H, PPh3), 7.81-8.02 (dd, 4H, J=7.6 Hz, aryl
H). 31P{1H} NMR (121.5 MHz, CDCl3): δ (ppm) 34.9 (s, 4P,
PPh3), 56.2 (s, 2P, ArPS2O). Selected IR (KBr, cm-1): 1985 (vs),
1586 (s), 1437 (s), 1242 (s), 1021 (s), 679 (s), 556 (s), 531 (m), 502
p-cymene)RuCl(μ-Cl)]2,29 and [Cp*Ru(OMe)]2 were prepared
30
according to literature methods. 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) were reported
with reference to SiMe4 (1H) and H3PO4 (31P). Infrared spectra
(KBr) were recorded on a Perkin-Elmer 16 PC FT-IR spectro-
photometer with the use of pressed KBr pellets, and positive FAB
mass spectra were recorded on a Finnigan TSQ 7000 spectrometer.
(s). MS (FAB): m/z 1744 [Mþ], 871 [1/2Mþ - 1], 843 [1/2Mþ
CO - 1]. Anal. Calcd for C88H74O6P6S4Ru2 (CH2Cl2) (C4H8O):
-
3
3
(19) Foreman, M. R., St. J.; Slawin, A. M. Z.; Woollins, J. D.
J. Chem. Soc., Dalton Trans. 1996, 3653–3657.
(20) Thomas, C. M.; Neels, A.; Stoeckli-Evans, H.; Suss-Fink, G.
C, 58.8; H, 4.55. Found: C, 58.2; H, 4.51.
Preparation of [Cp*Ru{(ArPS2O)2H}] CH2Cl2 0.5H2O (4
CH2Cl2 0.5H2O). To a slurry of Lawesson’s reagent (82 mg,
€
3
3
3
J. Organomet. Chem. 2001, 633, 85–90.
(21) Gray, I. P.; Milton, H. L.; Slawin, A. M. Z.; Woollins, J. D.
Dalton Trans. 2003, 3450–3457.
(22) Gray, I. P.; Slawin, A. M. Z.; Woollins, J. D. Z. Anorg. Allg.
Chem. 2004, 630, 1851–1857.
(23) Ly, T. Q.; Woollins, J. D. Coord. Chem. Rev. 1998, 176, 451–481,
and references therein.
(24) Leung, W. H.; Zheng, H.; Chim, J. L. C.; Chan, J.; Wong, W. T.;
Williams, I. D. J. Chem. Soc., Dalton Trans. 2000, 423–430.
(25) Zhang, Q. F.; Zheng, H.; Wong, W. Y.; Wong, W. T.; Leung,
W. H. Inorg. Chem. 2000, 39, 5255–5264.
(26) Leung, W. H.; Lau, K. K.; Zhang, Q. F.; Wong, W. T.; Tang,
B. Z. Organometallics 2000, 19, 2084–2089.
(27) Stephenson, T. A.; Wilkinson, G. J. Inorg. Nucl. Chem. 1966, 28,
945–956.
(28) Ahmad, N.; Levison, J. J.; Robinson, S. D.; Uttley, M. F.;
Wonchoba, E. R.; Parshall, G. W. Inorg. Synth. 1974, 15, 45–64.
(29) Bennett, M. A.; Huang, T. N.; Matheson, T. W.; Smith, A. K.
Inorg. Synth. 1982, 21, 75–92.
3
0.20 mmol) and 17% NH3 H2O (0.2 mL) in THF (10 mL) was
3
added a solution of [Cp*RuOMe]2 (107 mg, 0.20 mmol) in THF
(10 mL). The mixture was stirred at room temperature for 4 h.
The solvent was removed in vacuo, and the residue was recrys-
tallized from CH2Cl2/Et2O/hexane to give red crystalline solids
in five days at room temperature. Yield: 89 mg, 0.13 mmol, 29%
1
(based on Ru). H NMR (300 MHz, CDCl3): δ (ppm) 3.21 (s,
15H, Me), 3.72 (s, 6H, OCH3), 5.31 (s, 2H, CH2Cl2), 6.74 (d, 4H,
J=7.6 Hz, aryl H), 7.79-8.01 (dd, 4H, J=7.6 Hz, aryl H), 8.14
(br, 1H, POHOP). 31P{1H} NMR (121.5 MHz, CDCl3): δ (ppm)
96.4 (s). Selected IR (KBr, cm-1): 3274 (mbr), 1603 (s), 1430 (s),
1259 (s), 1029 (s), 678 (s), 556 (s), 531 (m), 504 (s). MS (FAB):
m/z 672 [Mþ - H - 1]. Anal. Calcd for C24H30O4P2S4Ru
3
(CH2Cl2) 0.5(H2O): C, 39.1; H, 4.33. Found: C, 38.5; H, 4.30.
Preparation of cis-[Ru{Fc(OMe)PS2}2(PPh3)2] (5). To a slurry of
[FcP(S)(μ-S)]2 (56 mg, 0.10 mmol) and CH3ONa (11 mg, 0.20 mmol)
3
(30) Koelle, U.; Kossakowski, J. Inorg. Synth. 1992, 29, 225–228.

2754 Organometallics, Vol. 29, No. 12, 2010
Wang et al.
Table 1. Crystallographic Data and Experimental Details for [(η6-p-cymene)Ru{μ-η1(S),η1(S,S 0)-ArP(S)S2}]2 (1), [Ru(μ-η1(O),η1(S),
η2(S,S 0)-ArPOS2)(PPh3)2]2 (2), [Ru(CO)(μ-η1(O),η2(S,S 0)-ArPOS2)(PPh3)]2 CH2Cl2 THF (3 CH2Cl2 THF), [Cp*Ru{(ArPS2O)2H}]
3
3
3
3
3
CH2Cl2 0.5H2O (4 CH2Cl2 0.5H2O), cis-[Ru(CO){Fc(OCH3)PS2}2(PPh3)] (6), cis-[Ru{Fc(OH)PS2}2(PPh3)2] CH2Cl2 3/4C6H14
3
3
3
3
3
(7 CH2Cl2 /4C6H14), and [(η6-p-cymene)Ru{η1(S),η2(S,S0)-FcPS2OP(S)SFc}] CH2Cl2 (9 CH2Cl2)
3
3
3
3
3
1
2
3 CH2Cl2 THF 4 CH2Cl2 0.5H2O
6
7 CH2Cl2 3/4C6H14
9 CH2Cl2
3
3
3
3
3
3
3
formula
fw
C34H42O2-
P2S6Ru2
939.12
16.4138(6)
21.4586(9)
21.3596(9)
90
94.724(2)
90
7497.7(5)
8
C86H74O4-
P6S4Ru2
1687.65
10.5303(1)
14.3653(1)
14.4226(1)
65.843(1)
85.502(1)
71.413(1)
1883.41(3)
1
C93H84O7-
Cl2P6S4Ru2
1900.70
14.1406(6)
15.1934(6)
24.0947(10)
89.176(2)
87.894(3)
63.428(2)
4626.7(3)
2
C25H33O4.5
P2Cl2S4Ru
767.66
12.8560(2)
22.4052(4)
23.8151(5)
90
90
90
6859.7(2)
8
-
C
41H39O3P3-
S4Fe2Ru
C
61.5H62.5O2-
Cl2P4S4Fe2Ru
C
31H34OCl2-
P2S4Fe2Ru
1013.64
12.7476(2)
21.9329(4)
14.8253(3)
90
95.300(1)
90
4127.31(13)
4
1407.32
45.4230(12)
11.9748(2)
22.3738(4)
90
104.942(2)
90
11758.3(4)
8
896.43
8.3220(1)
22.9333(3)
35.9063(4)
90
˚
a, A
˚
b, A
˚
c, A
R, deg
β, deg
γ, deg
90
90
3
˚
V, A
Z
6852.75(14)
8
cryst syst
space group
monoclinic
P21/n
1.664
296(2)
1.256
3808
69 864
17 066
0.0792
triclinic
P1
1.488
296(2)
0.692
864
35 128
8623
0.0321
triclinic
P1
1.364
296(2)
0.630
1948
86 057
21 222
0.0746
orthorhombic
Pbca
1.487
296(2)
0.979
3128
56 250
7795
0.0282
0.0397, 0.0700
0.0543, 0.1127
1.045
monoclinic
P21/c
1.631
296(2)
1.412
2056
41 800
9521
0.0732
monoclinic
C2/c
1.590
296(2)
1.181
5756
55 112
13 410
0.0779
orthorhombic
Pbca
1.738
296(2)
1.790
3616
54 745
7856
0.0440
0.0311, 0.0667
0.0421, 0.0711
1.023
F
T, K
calcd, g cm-3
3
μ, mm-1
F(000)
no. of reflns
no. of indep reflns
Rint
R1a, wR2b (I >2σ(I)) 0.0757, 0.1383 0.0290, 0.0649 0.0516, 0.1051
0.0445, 0.0868 0.0593, 0.1053
0.0680, 0.1025 0.0764, 0.1342
1.004
R1, wR2 (all data)
GoFc
0.0903, 0.1777 0.0374, 0.0691 0.0856, 0.1447
1.107
1.043
1.020
1.009
P
P
P
P
P
a R1 = ||Fo|- |Fc||/ |Fo|. b wR2 = [ w(|Fo2| - |Fc2|)2/ w|Fo2|2]1/2
.
c GoF = [ w(|Fo| - |Fc|)2/(Nobs - Nparam)]1/2
.
in methanol (8 mL) was added a solution of [Ru(PPh3)3Cl2] (192 mg,
0.20 mmol) in THF (10 mL). The mixture was heated at reflux for 2 h.
The solvent was removed in vacuo, and the residue was recrystallized
from CH2Cl2/hexane to give orange solids in three days at room
C5H4 in Fc), 5.30 (s, 2H, CH2Cl2), 7.26-7.85 (m, 30H, Ph), 8.14
(br, 2H, POH). 31P{1H} NMR (121.5 MHz, CDCl3): δ (ppm)
29.0 (s, 2P, FcPS2), 43.2 (s, 2P, PPh3). Selected IR (KBr, cm-1):
3139 (brs), 1636 (vs), 1384 (vs), 1184 (s), 1107 (vs), 1025 (m), 742
(m), 696 (s), 532 (m), 518 (m). MS (FAB): m/z 1268 [Mþ], 1006
[Mþ - PPh3], 744 [Mþ - 2PPh3]. Anal. Calcd for C56H50O2P4-
1
temperature. Yield: 128 mg, 0.10 mmol, 51% (based on Ru). H
NMR (300 MHz, CDCl3): δ (ppm) 3.91 (d, 6H, J=6.2 Hz, CH3),
4.38 (s, 10H, C5H5 in Fc), 4.49 (m, 8H, C5H4 in Fc), 7.26-7.43 (m,
30H, Ph). 31P{1H} NMR (121.5 MHz, CDCl3): δ (ppm) 41.2 (s, 2P,
PPh3), 105.4 (s, 2P, FcPS2). Selected IR (KBr, cm-1): 1602 (vs), 1381
(s), 1179 (s), 1023 (vs), 825 (m), 787 (s), 751 (m), 682 (s), 630 (m), 592
(s), 533 (m), 501 (s). MS (FAB): m/z 1248 [Mþ], 986 [Mþ - PPh3],
724 [Mþ - 2PPh3]. Anal. Calcd for C58H54O2P4S4Fe2Ru: C, 55.8; H,
4.36. Found: C, 55.6; H, 4.32.
S4Fe2Ru (CH2Cl2) (C4.5H10.5): C, 50.8; H, 4.48. Found: C,
50.5; H, 4.44.
Preparation of cis-[Ru(CO){Fc(OH)PS2}2(PPh3)] CH2Cl2
3
3
3
(8 CH2Cl2). Complex 8 was synthesized in a similar procedure
3
to 7 except that [RuHCl(CO)(PPh3)3] (188 mg, 0.20 mmol) was
used instead of [Ru(PPh3)3Cl2]. Orange crystalline solids of 8
3
CH2Cl2 were obtained by the recrystallization from CH2Cl2/
hexane in a week at room temperature. Yield: 91 mg, 0.09 mmol,
47% (based on Ru). 1H NMR (300 MHz, CDCl3): δ (ppm) 3.94
(d, 6H, J=6.2 Hz, CH3), 4.36 (s, 10H, C5H5 in Fc), 4.51 (m, 8H,
C5H4 in Fc), 5.31 (s, 2H, CH2Cl2), 7.23-7.41 (m, 15H, Ph), 8.21
(br, 2H, POH). 31P{1H} NMR (121.5 MHz, CDCl3): δ (ppm)
31.3 (s, 2P, FcPS2), 44.3 (s, 1P, PPh3). Selected IR (KBr, cm-1):
3216 (brs), 1948 (vs), 1631 (vs), 1382 (vs), 1189 (s), 1102 (s), 1021
(m), 748 (m), 684 (s), 535 (m), 516 (s). MS (FAB): m/z 985 [Mþ],
957 [Mþ - CO], 695 [Mþ - PPh3 - CO]. Anal. Calcd for
Preparation of cis-[Ru(CO){Fc(OMe)PS2}2(PPh3)] (6). To
a slurry of [FcP(S)(μ-S)]2 (56 mg, 0.10 mmol) and CH3ONa
(11 mg, 0.20 mmol) in methanol (10 mL) was added a solution of
[RuHCl(CO)(PPh3)3] (188 mg, 0.20 mmol) in THF (10 mL). The
mixture was heated at reflux for 2 h. The solvent was removed
in vacuo, and the residue was recrystallized from CH2Cl2/hexane
to afford orange crystals suitable for X-ray diffraction at room
temperature. Yield: 118 mg, 0.12 mmol, 59% (based on Ru). 1H
NMR (300 MHz, CDCl3): δ (ppm) 3.91 (d, 6H, J = 6.4 Hz,
CH3), 4.38 (s, 10H, C5H5 in Fc), 4.49 (m, 8H, C5H4 in Fc),
7.26-7.43 (m, 15H, Ph). 31P{1H} NMR (121.5 MHz, CDCl3): δ
(ppm) 43.6 (s, 1P, PPh3), 106.2 (s, 2P, FcPS2). Selected IR (KBr,
cm-1): 1946 (vs), 1607 (vs), 1385 (vs), 1183 (s), 1029 (vs), 827 (m),
785 (vs), 754 (m), 699 (s), 637 (m), 593 (s), 537 (m), 503 (s). MS
(FAB): m/z 1013 [Mþ], 985 [Mþ - CO], 723 [Mþ - PPh3 - CO].
Anal. Calcd for C41H39O3P3S4Fe2Ru: C, 48.6; H, 3.88. Found:
C, 48.4; H, 3.83.
C39H35O3P3S4Fe2Ru (CH2Cl2): C, 44.9; H, 3.40. Found: C,
3
45.2; H, 3.36.
Preparation of [(η6-p-cymene)Ru{η1(S),η2(S,S0)-FcPS2OP-
(S)SFc}] CH2Cl2 (9 CH2Cl2). To a fresh slurry of [FcP(S)(μ-
S)]2 (112 mg, 0.20 mmol) and 17% NH3 H2O (0.1 mL) in THF
3
3
3
(10 mL) was added an excess of NaHCO3 (101 mg, 1.20 mmol),
and then the mixture was heated at 60 °C for 1 h. The solid [(η6-
p-cymene)RuCl(μ-Cl)]2 (108 mg, 0.20 mmol) was added after the
solution had been cooled. The mixture was stirred at room
temperature for an additional 4 h, and the reddish-brown
solution was obtained. The solvent was removed in vacuo, and
the residue was washed with hexane and further recrystallized
from CH2Cl2/hexane at room temperature. Block orange crys-
Preparation of cis-[Ru{Fc(OH)PS2}2(PPh3)2] CH2Cl2 3/4-
3
3
C6H14 (7 CH2Cl2 3/4C6H14). To a slurry of [FcP(S)(μ-S)]2
(56 mg, 0.10 mmol) and 17% NH3 H2O (0.2 mL) in THF
3
3
3
(10 mL) was added the solid [Ru(PPh3)3Cl2] (192 mg, 0.20 mmol).
The mixture was stirred at room temperature overnight, and
a brown solution was obtained. The solvent was removed
in vacuo, and the residue was recrystallized from CH2Cl2/hexane
to give orange-red crystalline solids in a week at room tempera-
ture. Yield: 98 mg, 0.08 mmol, 47% (based on Ru). H NMR
(300 MHz, CDCl3): δ (ppm) 0.98 (s, CH3 in hexane), 1.31 (d, J=
6.4 Hz, CH2 in hexane), 4.26 (s, 10H, C5H5 in Fc), 4.38 (m, 8H,
tals of 9 CH2Cl2 suitable for X-ray diffraction were obtained in
3
1
five days. Yield: 147 mg, 0.18 mmol, 41% (based on Ru). H
NMR (300 MHz, CDCl3): δ (ppm) 1.34 (d, 6H, J = 6.8 Hz,
CH(CH3)2), 2.15 (s, 3H, PhCH3), 3.04 (septet, 1H, J=7.2 Hz,
CH(CH3)2), 4.45 (s, 10H, C5H5 in Fc), 4.52 (m, 8H, C5H4 in Fc),
5.32 (s, 2H, CH2Cl2), 5.40 and 5.68 (dd, 4H, J=7.6 Hz, C6H4).
1

Article
Organometallics, Vol. 29, No. 12, 2010 2755
31P{1H} NMR (121.5 MHz, CDCl3): δ (ppm) 107.1 (s, 1P,
FcP(S)S), 110.8 (s, 1P, FcPS2). Selected IR (KBr, cm-1): 1617
(vs), 1400 (vs), 1186 (s), 1024 (s), 875 (m), 781 (s), 757 (m), 706
(s), 673 (s), 561 (s), 502 (m), 463 (m). MS (FAB): m/z 811 [Mþ].
Scheme 1a
Anal. Calcd for C30H32OP2S4Fe2Ru (CH2Cl2): C, 41.5; H, 3.82.
3
Found: C, 41.2; H, 3.80.
X-ray Diffraction Measurements. Crystallographic data and
experimental details for 1, 2, 3 CH2Cl2 THF, 4 CH2Cl2 0.5H2O,
6, 7 CH2Cl2 3/4C6H14, and 9 CH2Cl2 are summarized in Table
3
3
3
3
3
3
3
1. Intensity data were collected on a Bruker SMART APEX
2000 CCD diffractometer using graphite-monochromated Mo
˚
KR radiation (λ=0.71073 A) at 293(2) K. The collected frames
were processed with the software SAINT.32 The data were
corrected for absorption using the program SADABS.31 Struc-
tures were solved by direct methods and refined by full-matrix
least-squares on F2 using the SHELXTL software package.33
All non-hydrogen atoms were refined anisotropically. The
positions of all hydrogen atoms were generated geometrically
˚
(Csp3-H=0.96, Csp2-H=0.93, and O-H=0.82 A), assigned
isotropic thermal parameters, and allowed to ride on their
respective parent carbon or oxygen atoms before the final cycle
of least-squares refinement. The solvent molecules such as
hexane in 7 CH2Cl2 3/4C6H14, dichloromethane in 3 CH2Cl2
3
3
3
3
THF, and water in 4 CH2Cl2 0.5H2O were isotropically refined
3
3
without hydrogen atoms due to disorder.
Results and Discussion
Cleavage of Lawesson’s reagent, [ArP(S)(μ-S)]2 (Ar=
p-CH3OC6H4), with sodium alkoxide normally generates
[ArP(OR)S2]-, which can act as the bidentate-S,S0 lig-
ands,19,20 in which the alkoxide group is usually involved
in the coordaintion of alkali metal alkoxides.14 Treatment of
[ArP(S)(μ-S)]2 with ammonium hydroxide (NH3 H2O) in a
3
THF solution resulted in a homogeneous slurry that con-
tained the [ArP(OH)S2]- species. The reactions between the
[ArP(OH)S2]- species and ruthenium compounds afforded a
series of new ruthenium-dithiophosphonate complexes, as
shown in Scheme 1. Interactions of [Ru(PPh3)3Cl2] and
[RuHCl(CO)(PPh3)3] with Lawesson’s reagent in the pre-
a Reagents and conditions: (i) [(η6-p-cymene)RuCl(μ-Cl)]2, THF, reflux;
(ii) NH3 H2O, THF, rt; (iii) [Ru(PPh3)3Cl2], THF, rt; (iv) [RuHCl-
3
(CO)(PPh3)3], THF, rt; (v) [(η5-Cp*)RuOMe]2, THF, rt.
Treatment of dimeric [(η6-p-cymene)RuCl(μ-Cl)]2 with Law-
esson’s reagent in the absence of NH3 H2O gave [(η6-
sence of NH3 H2O gave the dinuclear complexes [Ru(μ-
3
3
η1(O),η1(S),η2(S,S0)-ArPOS2)(PPh3)]2 (2) and [Ru(CO)(μ-
η1(O),η2(S,S0)-ArPOS2)(PPh3)]2 (3), respectively, in which
the [ArPOS2]2- ligands bridge two [Ru(PPh3)2]2þ in 2 and
two [Ru(CO)(PPh3)2]2þ in 3 via both the sulfur and oxygen
atoms. The IR spectra of complexes 2 and 3 show broad
absorption bands in the 1020-1045 cm-1 region, which are
assigned to the ν(P-O) vibration. The absorption bands in
the 675-680 cm-1 regions may be assigned to the ν(P-S)
vibration. The ν(CtO) stretching vibration was found at
1985 cm-1 in the IR spectrum of 3. The 31P{1H} NMR
spectra of the two complexes in CDCl3 show an intense
singlet (δ = 36.9 ppm for 2 and 34.9 ppm for 3) and a weak
singlet (δ=59.3 ppm for 2 and 56.2 ppm for 3), assignable to
PPh3 and [ArPOS2]2-, respectively. The positive ion FAB
mass spectra of the two complexes display the expected peaks
at m/z 1688 and 843 for 2 and m/z 1744 and 871 for 3,
corresponding to the molecular ions [Mþ] and [1/2Mþ - 1],
respectively, with the characteristic isotopic distribution
patterns.
p-cymene)Ru{μ-η1(S),η2(S,S0)-ArP(S)S2}]2 (1) as the sole iso-
lable product. The chlorides in the starting ruthenium compound
were substituted by the μ3-[ArP(S)S2]2- ligand. Reaction of [(η6-
p-cymene)RuCl(μ-Cl)]2 with Lawesson’s reagent in the presence
of NH3 H2O at room temperature or reflux gave an orange
3
powder that was difficult to characterize due to impurity.
Reaction of dimeric [Cp*RuCl(μ-Cl)]2 with Lawesson’s reagent
under similar conditions afforded a paramagnetic dark red solid,
presumably a ruthenium(III) species. Attempts to recrystallize
the dark red solid in different solvents were unsuccessful. Inter-
estingly, reaction of dimeric [Cp*Ru(OMe)]2 with Lawesson’s
reagent in the presence of NH3 H2O led to isolation of a
3
novel ruthenium(IV) complex, [Cp*Ru{(ArPS2O)2H}] (4), in
29% yield. In the present reaction, the methoxy groups in the
starting ruthenium compound were substituted by dithiopho-
sphonate ligands. The oxidation of Ru(II) to Ru(IV) was
probably caused by a disproportionation reaction because the
synthesis and workup were carried out under dinitrogen. The IR
spectrum of 1 shows the ν(PdS) and ν(P-S) stretching vibra-
tions at 685, 558, and 677 cm-1, respectively. The IR spectrum of
4 shows the unsymmetrical O-H O vibrational mode at 1259
(31) SMART and SAINTþ for Windows NT Version 6.02a; Bruker
Analytical X-ray Instruments Inc.: Madison, WI, 1998.
3 3 3
cm-1 and the ν(O-H) at 3274 cm-1 as a medium broad peak.
The 31P{1H} NMR spectra in CDCl3 exhibited a single reso-
nance at δ 84.1 ppm for 1 and 96.4 ppm for 4, indicating that
a single diastereomer was present for each of the complexes.
€
(32) Sheldrick, G. M. SADABS; University of Gottingen: Germany,
1996.
(33) Sheldrick, G. M. SHELXTL Software Reference Manual,
Version 5.1; Bruker AXS Inc.: Madison, WI, 1997.

2756 Organometallics, Vol. 29, No. 12, 2010
Wang et al.
Scheme 2a
gave [Ru{Fc(OH)2PS2}2(L0)(PPh3)] (L0 = PPh3 7, CO 8).
Complexes 7 and 8 are stable in the solid state but readily air
oxidized in solutions to give paramagnetic green species,
presumably ruthenium(III) complexes. The formation of
[FcP(OH)S2]- is due to the hydrolysis of [Fc(S)(μ-S)]2 by
the treatment of NH3 H2O. The 31P{1H} NMR spectra
3
show two intense singlets at δ 29.0 and 43.2 ppm for 7 and
δ 31.3 and 44.3 ppm for 8, assignable to [Fc(OH)PS2]- and
PPh3, respectively. The characteristic (P)O-H protons were
observed at δ 8.14 and 8.21 ppm in the 1H NMR spectra for
7 and 8, respectively, which were also confirmed by medium
broad peaks at 3139 and 3216 cm-1 in the IR spectra of 7 and
8, respectively. The IR spectra of 7 and 8 clearly show two
sets of bands at 1020-1110 and 680-750 cm-1, which may
be attributed to ν(P-O) and ν(P-S) absorptions, respectively.
The ν(CtO) stretching vibration was found at 1948 cm-1 in
the IR spectrum of 8. The positive ion FAB mass spectra show
the molecular ions at m/z 1268, 1006, and 744, which corre-
spond to the molecular ions [Mþ], [Mþ - PPh3], and [Mþ
-
2PPh3], respectively, and m/z 985, 957, and 695, which corre-
spond to the molecular ions [Mþ], [Mþ - CO], and [Mþ -
PPh3 - CO], respectively, with the characteristic isotopic distri-
bution patterns.
a Reagents and conditions: (i) MeONa, MeOH, rt; (ii) [Ru(PPh3)3Cl2]
or [RuHCl(CO)(PPh3)3], THF, rt; (iii) NH3 H2O, THF, rt; (iv) [Ru-
The [Fc(OH)PS(SH)] may be prepared in situ by the
hydrolysis of [FcP(S)(μ-S)]2 in the presence of an appropriate
3
amount of NH3 H2O. Interaction of [(η6-p-cymene)RuCl(μ-
(PPh3)3Cl2] or [RuHCl(CO)(PPh3)3], THF, rt; (v) NaHCO3, THF, 60 °C;
3
(vi) [(η6-p-cymene)RuCl(μ-Cl)]2, THF, rt.
Cl)]2 with in situ [Fc(OH)S(SH)] in the presence of excess
NaHCO3 under heating conditions followed by recrystalli-
zation from CH2Cl2/hexane gave [(η6-p-cymene)Ru{η1(S),
η2(S,S0)-FcPS2OP(S)SFc}] (9) in 41% yield. It seems that
treatment of [FcP(OH)S(SH)] with NaHCO3 at 60 °C re-
sulted in formation of Na2[(FcPS2)2O] probably due to eli-
mination of the water molecule.14,15 Further support for this
speculation comes from the X-ray crystallographic analysis
of 9. The 31P{1H} NMR spectrum of 9 displayed two intense
singlets at δ 107.1 and 110.8 ppm, which may be tentatively
assigned to the [FcP(S)SO-] and [FcPS2O-] moieties, re-
spectively. The 1H NMR spectrum of 9 shows the p-cymene
and ferrocenyl resonances with the expected relative inten-
sities and multiplicities. The IR spectrum of 9 clearly showed
three sets of strong bands at 1024 and 875, 781 and 757, and
673 and 561 cm-1, which may be attributed to ν(P-O),
ν(PdS), and ν(P-S) absorptions, respectively. The positive
ion FAB mass spectrum of 9 displays the expected peak at
m/z 811, which corresponds to the molecular ion [Mþ] with
the characteristic isotopic distribution pattern.
The positive ion FAB mass spectrum of 1 shows the molecular
ions [Mþ] and [1/2Mþ - 1] with the characteristic isotopic
distribution patterns. The molecular ion corresponding to the
loss of a hydride was observed in the FABþ mass spectrum of 4.
Encouraged by the previous reports on the ring-opening
reaction involving the well-known thionation of Lawesson’s
reagent,13-18 together with the successful isolation of the
above ruthenium-dithiophosphonato complexes, we set out
to study the reactions of ruthenium compounds such as [Ru-
(PPh3)3Cl2], [RuHCl(CO)(PPh3)3], and [(η6-p-cymene)RuCl-
(μ-Cl)]2 with the Lawesson’s reagent analogue [FcP(S)(μ-S)]2
(Fc=Fe(η5-C5H4)(η5-C5H5)) under the alcoholysis and hydro-
lysis conditions in the presence of the alkoxide or base, as shown
in Scheme 2. Similar to Lawesson’s reagent [ArP(S)(μ-S)]2,
dimeric [FcP(S)(μ-S)]2 reacts with two molar equivalents of
NaOR (R = Me, Et, n-Pr, and i-Pr) to give stable ferrocenyl-
phosphonodithiolate salts Na[FcP(OR)S2] that can bind to
various metals.21,22 With this in mind, [Ru(PPh3)3Cl2] or
[RuHCl(CO)(PPh3)3] reacted with Na[FcP(OMe)S2], derived
from [FcP(S)(μ-S)]2 with MeONa in methanol, giving the
neutral mononulcear complexes cis-[Ru{Fc(OCH3)2PS2}2-
(L0)(PPh3)] (L0 = PPh3 5, CO 6) isolated as air-stable, orange
crystals. The chlorides and one PPh3 ligand in [Ru(PPh3)3Cl2]
and the chloride and hydrogen atoms and two PPh3 moieties
in [RuHCl(CO)(PPh3)3] were substituted by [Fc(OCH3)PS2]-,
resulting in six-coordinate ruthenium(II) centers in 5 and 6. The
31P{1H} NMR spectra show two singlets at δ 41.2 and 105.4
ppm for 5 and δ 43.6 and 106.2 ppm for 6 assignable to the PPh3
and [Fc(OCH3)PS2]- ligands, respectively. The CtO stretching
vibration mode was found at 1946 cm-1 in the IR spectrum of 6.
The FABþ mass spectra of complexes 5 and 6 exhibit molecular
ions corresponding to [Mþ] and [Mþ - L0] (L0 =PPh3 and CO)
with the characteristic isotopic distribution patterns.
Crystal structures of 1, 2, 3 CH2Cl2 THF, 4 CH2Cl2
3
3
3
3
0.5H2O, 6, 7 CH2Cl2 3/4C6H14, and 9 CH2Cl2 have been
3
3
3
determined by single-crystal X-ray diffraction. In all seven
structures, the distances within dithiophosphonate ligands
agree well with those found in structurally characterized
dithiophosphonate complexes with other metal ions,11-22
which will not be discussed further. Selected bond lengths
and angles for 1, 2, 3 CH2Cl2 THF, 4 CH2Cl2 0.5H2O,
3
3
3
3
6, 7 CH2Cl2 3/4C6H14, and 9 CH2Cl2 are collected in
3
3
3
Tables 2-8, respectively.
Complex 1 crystallizedin the monoclinic space groupP21/n,
and the molecular structure of 1 is illustrated in Figure 1.
The neutral complex 1 comprises two [(η6-p-cymene)Ru]2þ
fragments bridged by two [ArP(S)S2]2- moieties via the
sulfur atoms. The molecular structure of 1 consists of dis-
crete dimeric molecules with distorted octahedral geome-
try around the ruthenium atom, having a p-cymene ring at
one face. One of the sulfur atoms of the dithiophosphato
Interaction of [Ru(PPh3)3Cl2] or [RuHCl(CO)(PPh3)3]
with dimeric [FcP(S)(μ-S)]2 in the presence of NH3 H2O in
THF followed by recrystallization from CH2Cl2/hexane
3

Article
Organometallics, Vol. 29, No. 12, 2010 2757
˚
˚
Table 2. Selected Bond Lengths (A) and Angles (deg) for
[(η6-p-cymene)Ru{μ-η1(S),η2(S,S 0)-ArP(S)S2}]2 (1)
Table 4. Selected Bond Lengths (A) and Angles (deg) for
[Ru(CO)(μ-η1(O),η2(S,S 0)-ArPOS2)(PPh3)]2 CH2Cl2 THF
3
3
(3 CH2Cl2 THF)a
3
3
molecule A
Ru(1)-S(2)
Ru(1)-S(5)
Ru(2)-S(2)
P(1)-S(1)
P(1)-S(3)
P(2)-S(5)
2.410(7)
2.433(8)
2.425(8)
2.040(12)
1.831(16)
2.047(12)
Ru(1)-S(4)
Ru(2)-S(1)
Ru(2)-S(4)
P(1)-S(2)
P(2)-S(4)
P(2)-S(6)
2.414(8)
2.433(8)
2.408(7)
2.106(10)
2.120(10)
1.845(16)
molecule B
Ru(1)-S(1)
Ru(1)-S(2)
Ru(1)-P(2)
Ru(1)-P(3)
Ru(1)-O(3)#1
Ru(1)-C(1)
P(1)-S(1)
2.4297(10)
2.4459(10)
2.3956(10)
2.4236(10)
2.206(2)
2.4302(10)
2.4459(10)
2.3910(10)
2.4096(11)
2.192(2)
S(2)-Ru(1)-S(4)
S(4)-Ru(1)-S(5)
S(4)-Ru(2)-S(1)
Ru(1)-S(2)-Ru(2)
P(1)-S(1)-Ru(2)
P(1)-S(2)-Ru(2)
P(2)-S(4)-Ru(1)
81.2(2)
79.8(3)
82.9(3)
98.7(3)
86.1(3)
84.8(3)
85.1(3)
S(2)-Ru(1)-S(5)
S(2)-Ru(2)-S(1)
S(4)-Ru(2)-S(2)
Ru(2)-S(4)-Ru(1)
P(1)-S(2)-Ru(1)
P(2)-S(4)-Ru(2)
P(2)-S(5)-Ru(1)
83.1(3)
79.6(3)
81.0(2)
99.1(3)
108.8(4)
108.7(4)
86.2(4)
1.801(4)
1.806(4)
2.0505(13)
2.0467(13)
1.517(2)
2.0383(13)
2.0453(13)
1.509(3)
P(1)-S(2)
P(1)-O(3)
C(1)-O(1)
1.151(5)
1.148(5)
S(1)-Ru(1)-S(2)
P(2)-Ru(1)-S(1)
P(3)-Ru(1)-S(1)
P(2)-Ru(1)-S(2)
P(3)-Ru(1)-S(2)
P(2)-Ru(1)-P(3)
O(3)#1-Ru(1)-S(1)
O(3)#1-Ru(1)-S(2)
O(3)#1-Ru(1)-P(2)
O(3)#1-Ru(1)-P(3)
C(1)-Ru(1)-S(1)
C(1)-Ru(1)-S(2)
C(1)-Ru(1)-P(2)
C(1)-Ru(1)-P(3)
C(1)-Ru(1)-O(3)#1
P(1)-S(1)-Ru(1)
P(1)-S(2)-Ru(1)
P(1)-O(3)-Ru(1)#1
Ru(1)-C(1)-O(1)
79.77(3)
84.72(3)
167.47(3)
164.42(4)
88.12(3)
107.45(4)
90.19(7)
88.98(7)
92.54(7)
86.37(7)
89.33(12)
89.00(13)
89.38(13)
93.68(13)
177.98(14)
90.27(4)
89.91(4)
144.09(15)
175.1(4)
79.75(3)
85.50(3)
166.90(4)
165.20(4)
87.38(4)
107.41(4)
91.45(7)
90.48(7)
91.02(7)
86.23(7)
88.10(13)
87.94(12)
90.47(12)
93.86(13)
178.41(14)
90.08(4)
89.48(4)
143.32(16)
174.5(4)
˚
Table 3. Selected Bond Lengths (A) and Angles (deg) for
[Ru(μ-η1(O),η1(S),η2(S,S 0)-ArPOS2)(PPh3)2]2 (2)a
Ru(1)-S(1)
Ru(1)-S(2)
Ru(1)-P(2)
P(1)-S(1)
2.4717(5)
2.4253(5)
2.3257(6)
2.0649(7)
1.5424(15)
Ru(1)-S(1)#1
Ru(1)-O(1)#1
Ru(1)-P(3)
P(1)-S(2)
2.4844(5)
2.2309(14)
2.3344(5)
2.0203(7)
P(1)-O(1)
S(1)-Ru(1)-S(2)
81.123(17) S(1)-Ru(1)-S(1)#1
82.071(17)
83.626(18)
170.974(19)
96.93(2)
S(2)-Ru(1)-S(1)#1 89.964(18) P(2)-Ru(1)-S(1)
P(2)-Ru(1)-S(1)#1 162.968(19) P(3)-Ru(1)-S(1)
P(3)-Ru(1)-S(1)#1 94.464(18) P(2)-Ru(1)-S(2)
P(3)-Ru(1)-S(2)
90.574(19) P(2)-Ru(1)-P(3)
O(1)#1-Ru(1)-S(1) 89.32(4) O(1)#1-Ru(1)-S(1)#1 73.96(4)
O(1)#1-Ru(1)-S(2) 162.35(4) O(1)#1-Ru(1)-P(2)
O(1)#1-Ru(1)-P(3) 97.76(4) Ru(1)-S(1)-Ru(1)#1
101.00(2)
96.72(4)
97.929(17)
80.14(2)
P(1)-S(1)-Ru(1)
P(1)-S(2)-Ru(1)
85.59(2) P(1)-S(1)-Ru(1)#1
87.80(2) P(1)-O(1)-Ru(1)#1
a Symmetry transformations used to generate equivalent atoms:
101.08(7)
a Symmetry transformations used to generate equivalent atoms:
#1 -x þ 1, -y, -z þ 2.
#1 -x þ 1, -y þ 2, -z þ 1.
˚
Table 5. Selected Bond Lengths (A) and Angles (deg) for
[Cp*Ru{(ArPS2O)2H}] CH2Cl2 0.5H2O (4 CH2Cl2 0.5H2O)
moiety is essentially symmetrically bonded to two ruthenium
atoms with distances Ru(1)-S(2) = 2.410(7) and Ru(2)-
S(2)=2.425(8) A, Ru(1)-S(4)=2.414(8) and Ru(2)-S(4)=
2.408(7) A, while S1 and S5 are bonded to the correspond-
ing ruthenium atoms with Ru-S distances of 2.433(8) and
2.433(8) A. Thus the two sulfur atoms of the bidentate dit-
hiophosphato ligands act as tricoordinate atoms in both
bridging and chelating modes.
Complex 2 crystallized in the triclinic space group P1, and
in the solid state 2 exists as a centrosymmetric dimer, as shown
in Figure 2. The neutral complex 2 comprises two [Ru-
(PPh3)2]2þ fragments symmetrically bridged by two [ArPOS2]2-
moieties via the sulfur and oxygen atoms. Two ruthenium
environments are identical, that is, each is surrounded by two
μ3-S, one μ-S, one μ-O, and two P atoms, forming a highly
distorted octahedral arrangement. The average Ru-μ3-S
3
3
3
3
Ru(1)-S(1)
Ru(1)-S(3)
P(1)-S(1)
P(2)-S(3)
P(1)-O(1)
O(1)-H(1)
2.4527(9)
2.4404(8)
2.0139(12)
2.0161(12)
1.533(3)
Ru(1)-S(2)
Ru(1)-S(4)
P(1)-S(2)
P(2)-S(4)
P(2)-O(2)
O(2)-H(1)
2.4371(9)
2.4573(9)
2.0143(12)
2.0195(12)
1.522(2)
˚
˚
˚
0.879(9)
1.603(9)
S(2)-Ru(1)-S(3)
S(3)-Ru(1)-S(1)
S(3)-Ru(1)-S(4)
P(1)-S(1)-Ru(1)
P(2)-S(3)-Ru(1)
80.26(3)
S(2)-Ru(1)-S(1)
S(2)-Ru(1)-S(4)
S(1)-Ru(1)-S(4)
P(1)-S(2)-Ru(1)
P(2)-S(4)-Ru(1)
76.92(3)
129.31(3)
82.08(3)
86.82(4)
86.52(4)
127.27(3)
76.88(3)
86.40(4)
87.05(4)
163.94(2)
O(1)-H(1) O(2)
3 3 3
The neutral complex 3 comprises two [Ru(CO)(PPh3)2]2þ
fragments symmetrically bridged by two [ArPOS2]2- moieties
via the sulfur and oxygen atoms. Two sulfur atoms in a
[ArPOS2]2- moiety chelate a ruthenium atom with a bite angle
S-Ru-S of 79.76(3)°. Each ruthenium atom is surrounded by
two μ-S, one μ-O, one C, and two P atoms, forming a highly
distorted octahedral configuration. The Ru-C bond length
˚
bond distance of 2.4780(5) A is slightly longer than the
average Ru-μ-S bond distance of 2.4253(5) A. The Ru-O
and Ru-P bond lengths in 2 are 2.2309(14) (av) and 2.3300(5)
(av) A, respectively. Four-membered ring Ru2S2 is coplanar,
˚
and the Ru Ru nonbonding distance is 3.738 A.
˚
˚
˚
and Ru-C-O bond angle in 3 are 1.804(4) A and 174.8(4)°,
3 3 3
Complex 3 CH2Cl2 THF crystallized in the triclinic
3
respectively, which are comparable to those in [RuH(CO)-
˚
3
space group P1 with centrosymmetry. The unit cell of
3 CH2Cl2 THF contains a molecule of 3 and disordered
{S2P(OEt)2}(PPh3)2] [Ru-C = 1.829(4) A and Ru-C-O =
175.4(4)°].10 The average Ru-P bond length of 2.405(1) A in 3
˚
3
3
˚
is also comparable to that of 2.3300(5) A in 2, whereas the bent
solvent molecules in the crystal lattice. There are two per-
pendicular arrangements of the molecules in the crystal with
slightly different conformations. No significant differences
in bonding parameters between these two molecules (A and
B) were found (see Table 4). The structure of one of the two
crystallographic independent molecules is shown in Figure 3.
angle P-O-Ru (av 143.70(15)°) in 3 is obviously bigger than
that in 2 (101.08(7)°). The Ru Ru nonbonding distance in 3
3 3 3
˚
is 5.469 A.
The solid-state structure of 4 has been established by X-ray
crystallography. The crystal of 4 CH2Cl2 0.5H2O crystallized
3
3

2758 Organometallics, Vol. 29, No. 12, 2010
Wang et al.
˚
Table 6. Selected Bond Lengths (A) and Angles (deg) for
cis-[Ru(CO){Fc(OCH3)PS2}2(PPh3)] (6)
Ru(1)-S(1)
Ru(1)-S(3)
Ru(1)-P(3)
P(1)-O(1)
C(21)-O(3)
2.4521(11)
2.5081(10)
2.3203(10)
1.590(3)
Ru(1)-S(2)
Ru(1)-S(4)
Ru(1)-C(21)
P(2)-O(2)
2.5458(11)
2.4356(10)
1.831(5)
1.591(3)
1.146(5)
S(1)-Ru(1)-S(2)
S(4)-Ru(1)-S(2)
S(4)-Ru(1)-S(3)
P(3)-Ru(1)-S(1)
P(3)-Ru(1)-S(2)
C(21)-Ru(1)-S(1)
C(21)-Ru(1)-S(3)
C(21)-Ru(1)-P(3)
P(1)-S(1)-Ru(1)
P(2)-S(3)-Ru(1)
S(1)-P(1)-S(2)
78.43(3)
91.80(4)
79.84(3)
94.06(4)
98.46(4)
98.67(13)
87.59(12)
87.98(12)
88.87(5)
S(3)-Ru(1)-S(2)
S(1)-Ru(1)-S(3)
S(4)-Ru(1)-S(1)
P(3)-Ru(1)-S(4)
P(3)-Ru(1)-S(3)
C(21)-Ru(1)-S(2)
C(21)-Ru(1)-S(4)
Ru(1)-C(21)-O(3)
P(1)-S(2)-Ru(1)
P(2)-S(4)-Ru(1)
S(3)-P(2)-S(4)
86.27(3)
92.60(4)
168.09(4)
94.12(3)
172.49(4)
173.08(12)
90.26(13)
176.2(4)
86.76(5)
88.24(4)
86.95(4)
104.34(6)
112.69(13)
113.31(12)
104.70(6)
114.40(12)
112.34(11)
O(1)-P(1)-S(1)
O(2)-P(2)-S(3)
O(1)-P(1)-S(2)
O(2)-P(2)-S(4)
Figure 1. Perspective view of [(η6-p-cymene)Ru{μ-η1(S),η2-
(S,S0)-ArP(S)S2}]2, 1.
˚
Table 7. Selected Bond Lengths (A) and Angles (deg) for
cis-[Ru{Fc(OH)PS2}2(PPh3)2] CH2Cl2 3/4C6H14
3
3
(7 CH2Cl2 3/4C6H14)
3
3
Ru(1)-S(1)
Ru(1)-S(3)
Ru(1)-P(3)
P(1)-S(1)
P(2)-S(3)
P(1)-O(1)
2.4645(14)
2.5368(12)
2.3046(12)
1.9970(19)
2.019(2)
Ru(1)-S(2)
Ru(1)-S(4)
Ru(1)-P(4)
P(1)-S(2)
P(2)-S(4)
P(2)-O(2)
2.5534(13)
2.4544(13)
2.3328(12)
2.016(2)
2.0042(18)
1.590(4)
1.586(4)
S(1)-Ru(1)-S(2)
S(4)-Ru(1)-S(2)
S(1)-Ru(1)-S(3)
P(3)-Ru(1)-S(1)
P(3)-Ru(1)-S(2)
P(3)-Ru(1)-S(3)
P(3)-Ru(1)-S(4)
P(3)-Ru(1)-P(4)
P(1)-S(2)-Ru(1)
P(2)-S(4)-Ru(1)
S(3)-P(2)-S(4)
O(1)-P(1)-S(2)
O(2)-P(2)-S(4)
77.13(5)
95.61(4)
93.42(5)
92.81(4)
169.15(5)
84.56(4)
93.62(4)
99.41(4)
82.63(6)
85.07(6)
101.53(7)
111.14(18)
114.88(18)
S(2)-Ru(1)-S(3)
S(4)-Ru(1)-S(3)
S(4)-Ru(1)-S(1)
P(4)-Ru(1)-S(1)
P(4)-Ru(1)-S(2)
P(4)-Ru(1)-S(3)
P(4)-Ru(1)-S(4)
P(1)-S(1)-Ru(1)
P(2)-S(3)-Ru(1)
S(1)-P(1)-S(2)
O(1)-P(1)-S(1)
O(2)-P(2)-S(3)
91.92(4)
77.26(4)
168.11(4)
98.73(5)
86.29(4)
166.98(5)
90.07(4)
85.34(6)
82.60(6)
102.47(8)
114.78(18)
110.42(19)
6
˚
Table 8. Selected Bond Lengths (A) and Angles (deg) for [(η -
p-cymene)Ru{η1(S),η2(S,S0)-FcPS2OP(S)SFc}] CH2Cl2 (9 CH2Cl2)
Figure 2. Perspective view of [Ru(μ-η1(O),η1(S),η2(S,S0)-ArPOS2)-
(PPh3)2]2, 2.
3
3
Ru(1)-S(1)
Ru(1)-S(3)
P(1)-S(2)
P(2)-S(4)
P(2)-O(1)
2.4640(7)
2.4440(6)
1.9913(9)
1.9399(10)
1.6533(18)
Ru(1)-S(2)
P(1)-S(1)
P(2)-S(3)
P(1)-O(1)
2.4460(7)
2.0049(9)
2.0294(9)
1.6074(18)
[N(Ph2PS)2],34 [Cp*Ru-(S2CNR2)2]Cl (R=Me, Et),9 [Cp*Ru-
(S2CNEt2)(S2CO)],9 and [Cp*RuCl2(η2-dithiolate)] (dithiolate=
S2CNR2, R =Me, Et; S2COiPr, S2P(OiPr)2),9 have been re-
ported to date. Complex 4 appears to be the first example of a
Cp*Ru(IV) complex containing dithiophosphonate ligands.
S(1)-Ru(1)-S(2)
S(2)-Ru(1)-S(3)
P(1)-S(2)-Ru(1)
S(1)-P(1)-S(2)
O(1)-P(1)-S(1)
O(1)-P(2)-S(3)
P(1)-O(1)-P(2)
79.37(2)
95.70(2)
83.53(3)
103.37(4)
111.39(7)
107.06(7)
129.48(11)
S(1)-Ru(1)-S(3)
P(1)-S(1)-Ru(1)
P(2)-S(3)-Ru(1)
S(3)-P(2)-S(4)
O(1)-P(1)-S(2)
O(1)-P(2)-S(4)
87.75(2)
82.79(3)
113.95(3)
116.43(5)
111.47(7)
107.64(7)
˚
The average Ru-S distance (2.4469(9) A) for 4 is longer than
those in [Cp*Ru(S2CNMe2)2][N(Ph2PS)2] (av 2.387(1) A),
34
˚
9
[Cp*Ru(S2CNMe2)2]Cl (av 2.33901(9) A), and [Cp*Ru-
˚
9
(S2CNEt2)(S2CO)] (av 2.3858(7) A). The dithiophospho-
˚
nate bite angles in 4 [range 76.88(3)-76.92(3)°] are obviously
larger than those of the dithiocarbamate [range 71.03(3)-
71.24(3)°] and dithiocarbonate [range 71.37(3)-72.04(3)°] in
[Cp*Ru(S2CNEt2)(S2CO)].9 Two P-O bonds in the dithio-
in the orthorhombic space group Pbca. A perspective view of
molecule 4 is shown in Figure 4. Complex 4 exhibits a four-
legged piano-stool configuration for the typical Ru(IV) mono-
cyclopentadienyl complexes, with coordination being to η5-
Cp* and two dithiophosphonates as bidentate ligands. It
should be noted that several non-hydrido Cp*Ru(IV) com-
plexes with dithiolate ligands, such as [Cp*Ru(S2CNMe2)2]-
˚
phosphonate ligands are 1.533(3) and 1.522(2) A, which are
in the range of the P-O single bond. The hydrogen atom of
the hydroxyl moiety is tentatively assigned to the O1 atom
˚
because the P(1)-O(1) of 1.533(3) A is slightly longer than
˚
the P(2)-O(2) of 1.522(2) A. A strong intramolecular hydro-
gen bond is observed in the dithiophosphonate ligands, as
˚
indicated by O(1) O(2) of 2.459(3) A with the O(1)-H-
(34) Cheung, W. M.; Zhang, Q. F.; Williams, I. D.; Leung, W. H.
Inorg. Chim. Acta 2006, 359, 782–788.
3 3 3
(1) O(2) angle of 163.94(2)°.
3 3 3

Article
Organometallics, Vol. 29, No. 12, 2010 2759
Figure 5. Perspective view of cis-[Ru(CO){Fc(OCH3)PS2}2-
(PPh3)], 6.
Figure 3. Perspective view of [Ru(CO)(μ-η1(O),η2(S,S0)-ArPOS2)-
(PPh3)2]2, 3.
Figure 4. Perspective view of [Cp*Ru{(ArPS2O)2H}], 4.
The molecular structure of 6 is shown in Figure 5. The
geometry around ruthenium is pseudo-octahedral with two
cis-chelating [Fc(OCH3)PS2]- ligands. The chelating S-
Ru-S angles are considerably reduced [78.43(3)° and
79.84(3)°] due to the small bite of the dithio ligands. The
four-membered RuS2P rings are nonplanar. Each ring con-
tains a pair of long and short Ru-S bonds [Ru(1)-S(2) =
Figure 6. Perspective view of cis-[Ru{Fc(OH)PS2}2(PPh3)2], 7.
form the basal plane. The four-membered RuS2P rings are
nonplanar and distorted with the average chelating S-Ru-S
angle of 77.20(5)°. Each ring contains a pair of long and short
Ru-S bonds. A similar case was observed in cis-[Ru{S2P-
˚
˚
2.5458(11) A (“long”) withRu(1)-S(1)=2.4521(11) A (“short”);
(OEt)2}2(PPh3)2].10 The average Ru-S bond length in 7
3
˚
Ru(1)-S(3) = 2.5081(10) A (“long”) with Ru(1)-S(4) =
CH2Cl2 3/4C6H14 (av 2.5023(13) A) is comparable to that in
˚
3
˚
2.4356(10) A (“short”)]. The average Ru-S bond length in
˚
cis-[Ru{S2P(OEt)2}2(PPh3)2] (av 2.4974(11) A) with the che-
6 (av 2.4854(11) A) is comparable to that in 7 CH2Cl2 3/4-
˚
lated dithiophosphate ligands,10 but slightly longer than that
3
3
˚
C6H14 (av 2.5023(13) A). Among the unequal R-S bonds in
four-membered RuS2P rings for 6, the Ru(1)-S(2) bond
(2.5458(11) A) trans to CO in 6 is elongated due to π back-
˚
in cis-[Ru(S2CNEt2)2(PPh3)2] (av 2.3952(5) A) with chelated
dithiocarbamate ligands.36 The average Ru-P bond length
˚
of 2.3187(12) A in 7 CH2Cl2 3/4C6H14 agrees well with those
˚
3
3
bonding from the CtO bond. The Ru-P bond length of
in some related ruthenium(II)-PPh3 complexes.5,10,35,36
X-ray structural analysis revealed that 9 CH2Cl2 crystal-
2.3203(10) A in 6 agrees well with those in 7 CH2Cl2 3/4-
˚
3
3
3
C6H14 and some other related ruthenium(II) complexes with
PPh3 ligands.5,10,35 The Ru-C bond length of 1.831(5) A in 6
lized in the orthorhombic space group Pbca, consisting of
one neutral complex and one CH2Cl2 solvent molecule. The
molecular structure of 9 is shown in Figure 7. The central
ruthenium atom in 9 exists in a distorted octahedral coordi-
nation environment, with the phenyl ring of the p-cymene ligand
formally occupying three octahedral sites. The [FcPS2OP-
(S)SFc]2- ligand is bonded to the metal center via three sulfur
atoms to complete the coordination sphere. [FcPS2OP(S)-
SFc]2- acts as an unsymmetrical tridentate ligand to form
˚
is normal for the ruthenium-carbonyl complexes.8,10
X-ray structural analysis revealed that 7 CH2Cl2 3/4-
3
3
C6H14 crystallized in the monoclinic space group C2/c,
consisting of neutral complex and disorder solvent molecules
that are consistent with the microanalytical and NMR data.
The molecular structure of 7 is shown in Figure 6. Two cis
PPh3 ligands bind to the ruthenium center with the P-Ru-P
angle of 99.41(4)°, and two chelating [Fc(OH)PS2]- ligands
(35) Das, A. K.; Peng, S. M.; Bhattacharya, S. J. Chem. Soc., Dalton
Trans. 2000, 181–184.
(36) Critchow, P. B.; Robinson, S. D. J. Chem. Soc., Dalton Trans.
1975, 1367–1372.

2760 Organometallics, Vol. 29, No. 12, 2010
Wang et al.
ligands were synthesized and characterized structurally and
spectroscopically. The dinuclear neutral complexes, [Ru(μ-
η1(O),η1(S),η2(S,S0)-ArPOS2)(PPh3)2]2 and [Ru(CO)(μ-η1-
(O),η2(S,S0)-ArPOS2)(PPh3)]2, were obtained from the
reactions of [Ru(PPh3)3Cl2] and [RuHCl(CO)(PPh3)3], respec-
tively, with Lawesson’s reagent in the presence of ammo-
nium hydroxide. The mononuclear ruthenium(IV) complex
[Cp*Ru{(ArPS2O)2H}] with a four-legged piano-stool geo-
metry was synthesized from the reaction of dimeric [Cp*Ru-
(OMe)]2 with Lawesson’s reagent in the presence of ammo-
nium hydroxide. Similarly, the mononuclear ruthenium(II)
complexes [Ru{Fc(OH)2PS2}2(L0)(PPh3)] (L0 = PPh3, CO)
were isolated from interaction of [Ru(PPh3)3Cl2] or
[RuHCl(CO)(PPh3)3] with dimeric [FcP(S)(μ-S)]2 in the pre-
sence of ammonium hydroxide. The mononuclear neutral
complex [(η6-p-cymene)Ru{η1(S),η2(S,S0)-FcPS2OP(S)SFc}]
was formed via the elimination of water from the [FcP-
(OH)S(SH)] intermediate in the presence of NaHCO3. It is
interesting to note that [FcPS2OP(S)SFc]2- acts as an unsym-
metrical tridentate ligand to form one four-membered chelate
ring RuS2P and two six-membered rings RuS2P2O. The initial
aim of this work was to demonstrate the versatile coordination
of the phosphonodithioates formed under different conditions
and to study their reactivity as ligands with the typical rut-
henium(II) starting complexes. The study of the reactivity of
ruthenium-phosphonodithioate complexes toward unsaturated
organic substrates is underway in this laboratory.
Figure 7. Perspective view of [(η6-p-cymene)Ru{η1(S),η2(S,S0)-
FcPS2OP(S)SFc}], 9.
one four-membered chelate ring RuS2P with a S(1)-Ru-
(1)-S(2) bite angle of 79.37(2)° and the two six-membered
rings RuS2P2O with S(1)-Ru(1)-S(3) angle of 87.75(2)° and
S(2)-Ru(1)-S(3) angle of 95.70(2)°. The three Ru-S bonds
are approximately equal in length [Ru(1)-S(1)=2.4640(7),
˚
Ru(1)-S(2) =2.4460(7), and Ru(1)-S(3) =2.4440(6) A], and
the corresponding three P-S bonds are also equal in length
[P(1)-S(1) = 2.0049(9), P(1)-S(2) = 1.9399(10), and P(2)-
S(3) = 2.0294(9) A], suggesting that the [FcPS2OP(S)SFc]
2-
˚
Acknowledgment. This project was supported by the
Natural Science Foundation of China (20771003) and
the Program for New Century Excellent Talents in the
University of China (NCET-06-0556).
moiety has a partial π character. The average Ru-S bond
length in 9 [av 2.4513(7) A] is slightly shorter than those in 6
˚
[av 2.4854(11) A] and 7 CH2Cl2 3/4C6H14 [av 2.5023(13) A].
˚
˚
3
3
˚
The P(2)-S(4) bond length of 1.9399(10) A in 9 indicates a
considerable double-bond character, which is supported by a
strong absorption at 781 cm-1 due to the stretching vibration
of the PdS double bond shown in the IR spectrum of 9. The
[FcPS2OP(S)SFc]2- ligand contains a nonlinear P(1)-O-
(1)-P(2) linkage with an angle of 129.48(11)°.
Supporting Information Available: Listings of final atomic co-
ordinates, anisotropic displacement parameters, and bond
lengths and angles for complexes 1, 2, 3 CH2Cl2 THF, 4
3
3
3
CH2Cl2 0.5H2O, 6, 7 CH2Cl2 3/4C6H14, and 9 CH2Cl2. This
3
3
3
3
In summary, a series of ruthenium complexes containing
the dithiophosphonates [Ar(RO)PS2]- and [Fc(RO)PS2]-
material is available free of charge via the Internet at http://
pubs.acs.org.