Synthesis and reactivity of ruthenium complexes with 1,1′-dithiolate ligands

Article abstract of DOI:10.1016/j.jorganchem.2009.04.026

Reactions of [Ru(PPh₃)₃Cl₂] with ROCS₂K in THF at room temperature and at reflux gave the kinetic products trans-[Ru(PPh₃)₂(S₂COR)₂] (R = ⁿPr 1, ⁱ

Full text of DOI:10.1016/j.jorganchem.2009.04.026

Journal of Organometallic Chemistry 694 (2009) 3844–3851
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis and reactivity of ruthenium complexes with 1,10-dithiolate ligands
c
Fang-Hui Wu a,b, Taike Duan a, Lude Lu b, Qian-Feng Zhang a, , Wa-Hung Leung
*
a Institute of Molecular Engineering and Applied Chemistry, Anhui University of Technology, 59 Hudong Road, Ma’anshan, Anhui 243002, PR China
b Material Chemistry Laboratory, Nanjing University of Science and Technology, Nanjing 210094, PR China
c Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Reactions of [Ru(PPh3)3Cl2] with ROCS2K in THF at room temperature and at reflux gave the kinetic prod-
ucts trans-[Ru(PPh3)2(S2COR)2] (R = nPr 1, iPr 2) and the thermodynamic products cis-[Ru(PPh3)2(S2COR)2]
Received 6 March 2009
Received in revised form 20 April 2009
Accepted 21 April 2009
Available online 3 May 2009
i
(R = nPr 3, Pr 4), respectively. Treatment of [RuHCl(CO)(PPh3)3] with ROCS2K in THF afforded [RuH(CO)-
(S2COR)(PPh3)2] (R = nPr 5, iPr 6) as the sole isolable products. Reaction of [RuCl2(PPh3)3] with tetrameth-
ylthiuram disulfide [Me2NCS2]2 gave a Ru(III) dithiocarbamate complex, [Ru(PPh3)2(S2CNMe2)Cl2] (7).
This reaction involved oxidation of ruthenium(II) to ruthenium(III) by the disulfide group in [Me2NCS2]2.
Treatment of 7 with 1 equiv. of [M(MeCN)4][ClO4] (M = Cu, Ag) gave the stable cationic ruthenium(III)–
alkyl complexes [Ru{C(NMe2)QC(NMe2)S}(S2CNMe2)(PPh3)2][ClO4] (Q = O 8, S 9) with ruthenium–carbon
bonds. The crystal structures of complexes 1, 2, 4ꢀCH2Cl2, 6, 7ꢀ2CH2Cl2, 8, and 9ꢀ2CH2Cl2 have been deter-
mined by single-crystal X-ray diffraction. The ruthenium atom in each of the above complexes adopts a
pseudo-octahedral geometry in an electron-rich sulfur coordination environment. The 1,10-dithiolate
ligands bind to ruthenium with bite S–Ru–S angles in the range of 70.14(4)–71.62(4)°. In 4ꢀCH2Cl2, the
P–Ru–P angle for the mutually cis PPh3 ligands is 103.13(3)°, the P–Ru–P angles for other complexes with
mutually trans PPh3 ligands are in the range of 169.41(4)–180.00(6)°. The alkylcarbamate
[C(NMe2)QC(NMe2)S]ꢁ (Q = O, S) ligands in 8 and 9 are planar and bind to the ruthenium centers via
the sulfur and carbon atoms from the C@S and N@C double bonds, respectively. The Ru–C bond lengths
are 1.975(5) and 2.018(3) Å for 8 and 9ꢀ2CH2Cl2, respectively, which are typical for ruthenium(III)–alkyl
complexes. Spectroscopic properties along with electrochemistry of all complexes are also reported in the
paper.
Keywords:
Ruthenium
Sulfur
1,10-Dithiolate
Phosphine
Synthesis
Crystal structure
Ó 2009 Published by Elsevier B.V.
1. Introduction
[Ru(S2COR)2(PPh3)2] (R = Et, iPr) [10], cis-[Ru{S2P(OEt)2}2(PPh3)2]
[11], cis-[Ru(S2CSCH2Ph2)2(PPh3)2] [12] and cis-[Ru(S2CSC5HF4)2-
Transition metal–sulfur complexes are of significance because
of diverse bonding possibilities and their roles in homogeneous
catalysis [1]. Of particular interest are ruthenium–sulfur com-
plexes that may serve as functional models for Fe–S proteins due
to the periodic relationship between ruthenium and iron [2]. In re-
cent years there has been an increasing interest in ruthenium com-
plexes with sulfur-donor ligands, in part because of the high
catalytic activity of RuS2 in various hydrotreating processes [3]. It
may be thus understood that a number of organometallic and clas-
sical coordination complexes of ruthenium with thiolate and dithio
(PPh3)2] [13]. Charavorty and coworkers have studied the redox
properties of these complexes and found that a coordination rear-
rangement along with the redox process occurs in oxidation-in-
duced cis–trans isomerization of these complexes [14]. It was
found that the preferred geometry is cis for ruthenium (II) and
trans for ruthenium(III) [15]. The cis to trans isomerization process
in the ruthenium species [Ru(S2COiPr)2(PPh3)2]0/+ has recently
been re-investigated by Takagi and coworkers [10]. Electrochemi-
cal oxidation at various concentrations of PPh3 in the bulk solution
gives both complexes cis-[Ru(S2COiPr)2(PPh3)2] with d6-ruthe-
nium(II) and trans-[Ru(S2COiPr)2(PPh3)2]+ with d5-ruthenium(III)
have been isolated and structurally characterized. As a matter of
fact, the formation of the cis-[Ru(S,S)2(PPh3)2] complexes strongly
supports the cis stereochemistry predicted for the starting com-
pound. Remarkably, with a less bulky phosphine ligand, PMe2Ph,
the trans isomers trans-[Ru(S2COEt)2(PMe2Ph)2] [16] and trans-
[Ru(S2PEt2)2(PMe2Ph)2] [17] with d6-ruthenium(II) centers were
isolated. However, the ruthenium complexes with dithio ligands
have been relatively less explored. In efforts to develop
ꢁ
acids (R2NCS2ꢁ, ROCS2ꢁ, RCS2ꢁ, R2PS2 and (RO)2PS2ꢁ) have been
synthesized and their reactivity investigated [4–6]. For example,
the reaction of [Ru(PPh3)3Cl2] with alkaline salts of 1,1-dithiolates
gave the complexes [Ru(S,S)2(PPh3)2] which have the phosphines
mutually cis [4]. The reported type cis-[Ru(S,S)2(PPh3)2] complexes
include cis-[Ru(S2CNR2)2(PPh3)2] (R = Me, Et, nPr, iPr) [7–9], cis-
* Corresponding author. Tel./fax: +86 555 2312041.
E-mail address: zhangqf@ahut.edu.cn (Q.-F. Zhang).
0022-328X/$ - see front matter Ó 2009 Published by Elsevier B.V.
doi:10.1016/j.jorganchem.2009.04.026

F.-H. Wu et al. / Journal of Organometallic Chemistry 694 (2009) 3844–3851
3845
ruthenium-1,10-dithiolate-based complexes for redox catalysis
[18,19], we sought to investigate the reaction chemistry, e.g. oxida-
tion reactions and structural variation, of ruthenium–sulfur com-
plexes. We report here the synthesis, reactivity, and crystal
structures ofꢁthe ruthenium complexes with the 1,10-dithiolate li-
1241 (vs), 1094 (s), 1043 (m), 745 (m), 693 (s), 540 (m), 521 (m).
Anal. Calc. for C44H43O2P2S4Ruꢀ(CH2Cl2): C, 55.1; H, 4.63. Found:
C, 54.7; H, 4.61%. For 4: Yield: 77 mg, 55%. 1H NMR (300 MHz,
CDCl3): d 1.13–2.28 (m, 12H, –CH3), 5.15 (m, 2H, –CH–), 7.01–
7.27 (m, 30H, –C6H5) ppm. 31P{1H} NMR (121.5 MHz, CDCl3): d
38.4 (s) ppm. IR (KBr, cmꢁ1): 1631 (vs), 1238 (vs), 1091 (s), 1046
(m), 745 (m), 692 (s), 543 (m), 518 (m). Anal. Calc. for
C44H43O2P2S4Ruꢀ(CH2Cl2): C, 55.1; H, 4.63. Found: C, 54.6; H, 4.58%.
ꢁ
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gands ROCS2 and R2NCS2 (R = Me, nPr, Pr).
2. Experimental
2.4. Synthesis of [RuH(CO)(PPh3)2(S2COR)] (R = nPr 5, Pr 6)
i
2.1. General
A mixture of [RuHCl(CO)(PPh3)3] (150 mg, 0.16 mmol) and
nPrOCS2K (28 mg, 0.16 mmol) or iPrOCS2K (28 mg, 0.16 mmol)
was dissolved in THF (20 mL) and then stirred overnight at room
temperature. A color change from yellow to pale orange was ob-
served. The solvent was pumped off and the residue was washed
with hexane and further recrystallized from CH2Cl2/hexane. Yellow
block crystals of 5 or 6 were obtained in three days. For 5: Yield:
72 mg, 52%. 1H NMR (300 MHz, CDCl3): d 0.89 (t, 3H, –CH3), 1.57
(s, 1H, RuH), 2.27 (m, 2H, –CH2–), 2.81–3.14 (m, 2H, –CH2O–),
7.33–7.61 (m, 30H, –C6H5) ppm. 31P{1H} NMR (121.5 MHz, CDCl3):
d 41.4 (s) ppm. IR (KBr, cmꢁ1): 1935 (vs), 1636 (vs), 1237 (vs), 1090
(s), 1038 (m), 738 (m), 694 (s), 536 (m), 523 (m). Anal. Calc. for
C41H38O2P2S2Ru: C, 62.3; H, 4.85. Found: C, 61.6; H, 4.82%. For 6:
Yield: 69 mg, 50%. 1H NMR (300 MHz, CDCl3): d 0.93 (t, 6H,
–CH3), 1.63 (s, 1H, RuH), 5.12 (m, 4H, –CH2–), 7.29–7.63 (m, 30H,
–C6H5) ppm. 31P{1H} NMR (121.5 MHz, CDCl3): d 40.6 (s) ppm. IR
(KBr, cmꢁ1): 1942 (vs), 1634 (vs), 1232 (vs), 1085 (s), 1034 (m),
741 (m), 696 (s), 542 (m), 528 (m). Anal. Calc. for C41H38O2P2S2Ru:
C, 62.3; H, 4.85. Found: C, 62.1; H, 4.79%.
All synthetic manipulations were carried out under dry nitrogen
by standard Schlenk techniques. Solvents were purified, distilled
and degassed by standard methods. [Ru(PPh3)3Cl2] [20], [RuHCl
(CO)(PPh3)3] [21], [Cu(MeCN)4][ClO4] [22] were prepared according
to the literature methods. [Ag(MeCN)4][ClO4] was obtained from
the reaction of Ag2O and HClO4 in MeCN solution. Potassium xan-
thates ROCS2K (R = Pr and iPr) were synthesized from the reactions
of CS2 and KOH in ROH. Tetramethylthiuram disulfide was pur-
chased from Alfa Ltd. and used as received. NMR spectra were re-
corded on a Bruker ALX 300 spectrometer operating at 300 and
121.5 MHz for 1H and 31P, respectively. Chemical shifts (d, ppm)
were reported with reference to SiMe4 (1H) and H3PO4 (31P). Infra-
red spectra (KBr) were recorded on a Perkin–Elmer 16 PC FT-IR
spectrophotometer. Cyclic voltammetry was performed with on a
CHI 660 electrochemical analyzer. A standard three-electrode cell
was used with glassy carbon working electrode, a platinum coun-
ter electrode and Ag/AgCl reference electrode under an nitrogen
atmosphere at 25 °C. Formal potentials (E°) were measured in
CH2Cl2 solutions with 0.1 M [nBu4N]PF6 as supporting electrolyte
and reported with reference to the ferrocenium–ferrocene couple
(Cp2Fe+/0). In the ꢁ1.5 to +1.2 V region, a potential scan rate of
100 mV sꢁ1 was used. Elemental analyses were carried out using
a Perkin–Elmer 2400 CHN analyzer.
2.5. Synthesis of [Ru(S2CNMe2)(PPh3)2Cl2]ꢀ2CH2Cl2 (7ꢀ2CH2Cl2)
To a solution of [Ru(PPh3)3Cl2] (144 mg, 0.15 mmol) in THF
(20 mL) at 0 °C was added tetramethylthiuram disulfide (24 mg,
0.10 mmol), and the mixture was stirred overnight at room tem-
perature. The resulting green solution was evaporated to dryness,
and the residue was recrystallized from CH2Cl2/hexane to give dark
green crystals. Yield: 56 mg, 43%. FT-IR (KBr, cmꢁ1): 1531 (vs),
1434 (s), 1106 (s), 997 (s), 910 (m), 741 (w), 694 (s), 595 (m),
i
2.2. Synthesis of trans-[Ru(PPh3)2(S2COR)2] (R = nPr 1, Pr 2)
A mixture of [Ru(PPh3)3Cl2] (144 mg, 0.15 mmol) and 2 equiv. of
i
nPrOCS2K (53 mg, 0.30 mmol) or PrOCS2K (53 mg, 0.30 mmol) in
THF (20 mL) was stirred at room temperature for 2 h. The sol-
vent was pumped off and the residue was recrystallized from
CH2Cl2/Et2O at ꢁ10 °C to give orange crystalline solids in two days.
For 1: Yield: 63 mg, 45%. 1H NMR (300 MHz, CDCl3): d 1.12 (t, 6H,
–CH3), 2.38 (m, 4H, –CH2–), 4.48 (t, 4H, –CH2O–), 7.02–7.28 (m,
30H, –C6H5) ppm. 31P{1H} NMR (121.5 MHz, CDCl3): d 46.8 (s)
ppm. IR (KBr, cmꢁ1): 1637 (vs), 1244 (vs), 1096 (s), 1040 (m),
741 (m), 697 (s), 536 (m), 520 (m). Anal. Calc. for C44H44O2P2S4Ru:
C, 59.0; H, 4.95. Found: C, 58.7; H, 4.91%. For 2: Yield: 56 mg, 41%.
1H NMR (300 MHz, CDCl3): d 1.15–2.24 (m, 12H, –CH3), 5.14 (m,
2H, –CH–), 7.08–7.26 (m, 30H, –C6H5) ppm. 31P{1H} NMR
(121.5 MHz, CDCl3): d 45.7 (s) ppm. IR (KBr, cmꢁ1): 1635 (vs),
1241 (vs), 1093 (s), 1042 (m), 744 (m), 690 (s), 546 (m), 522 (m).
Anal. Calc. for C44H44O2P2S4Ru: C, 59.0; H, 4.95. Found: C, 58.3;
H, 4.94%.
520 (s).
leff = 1.91 lB at 296 K. Anal. Calc. for C39H36NCl2P2S2-
Ruꢀ2(CH2Cl2): C, 49.9; H, 4.09; N, 1.42. Found: C, 49.5; H, 4.01,
N, 1.44%.
2.6. Synthesis of [Ru{C(NMe2)OC(NMe2)S}(S2CNMe2)(PPh3)2][ClO4] (8)
To a solution of complex 7 (82 mg, 0.01 mmol) in CH2Cl2
(10 mL) was added
a solution of [Cu(MeCN)4][ClO4] (33 mg,
0.10 mmol) in MeCN (3 mL), and the mixture was stirred for 4 h
at room temperature. The crude product was filtered out and
washed with hexane. Deep green crystals of 8 were obtained by
recrystallization of the crude product from CH2Cl2/Et2O in a week.
Yield: 44 mg, 57%. FT-IR (KBr, cmꢁ1): 1594 (vs), 1395 (m), 1167 (s),
1098 (s), 1157 (m), 986 (m), 747 (m), 696 (s), 632 (m), 589 (m), 523
(s), 408 (s). leff = 1.92 lB at 296 K. Anal. Calc. for C45H48N3O5ClP2S3-
Ru: C, 53.7; H, 4.81; N, 4.18. Found: C, 52.9; H, 4.76, N, 4.14%.
i
2.3. Synthesis of cis-[Ru(PPh3)2(S2COR)2] (R = nPr 3, Pr 4)
2.7. Synthesis of [Ru{C(NMe2)SC(NMe2)S}(S2CNMe2)(PPh3)2][ClO4]ꢀ
2CH2Cl2 (9ꢀ2CH2Cl2)
A mixture of [Ru(PPh3)3Cl2] (144 mg, 0.15 mmol) and 2 equiv. of
i
nPrOCS2K (53 mg, 0.30 mmol) or PrOCS2K (53 mg, 0.30 mmol) in
THF (20 mL) was heated at reflux for 2 h. The solvent was pumped
off and the residue was recrystallized from CH2Cl2/Et2O to give red
crystalline solids in a week. For 3: Yield: 89 mg, 64%. 1H NMR
(300 MHz, CDCl3): d 0.97 (t, 6H, –CH3), 2.15 (m, 4H, –CH2–), 4.22
(t, 4H, –CH2O–), 7.11–7.26 (m, 30H, –C6H5) ppm. 31P{1H} NMR
(121.5 MHz, CDCl3): d 39.2 (s) ppm. IR (KBr, cmꢁ1): 1639 (vs),
To a solution of complex 7 (82 mg, 0.10 mmol) in CH2Cl2
(15 mL) was added
a solution of [Ag(MeCN)4][ClO4] (38 mg,
0.10 mmol) in MeCN (3 mL), and the mixture was stirred for
0.5 h at room temperature. The solvent was pumped off and the
residue was washed with hexane and further recrystallized from
CH2Cl2/Et2O. Brown green crystals were obtained in three days.

3846
F.-H. Wu et al. / Journal of Organometallic Chemistry 694 (2009) 3844–3851
Yield: 38 mg, 49%. FT-IR (KBr, cmꢁ1): 1591 (vs), 1397 (m), 1156
(m), 1094 (s), 989 (m), 751 (m), 700 (s), 585 (m), 526 (s), 451
ture. With longer reaction time and at higher temperature at
80 °C, trans-[Ru(PPh3)2(S2COR)2] isomerized to the thermodynamic
products cis-[Ru(PPh3)2(S2COR)2]. The course of reaction between
[Ru(PPh3)3Cl2] and nPrOCS2K was followed by 31P NMR spectros-
copy. Initially, only one resonance peak at 46.8 ppm due to the
trans complex was found for the reaction mixture. After the solu-
tion was allowed to stand for 1 day under heating condition, a
new 31P signal at 39.2 ppm probably attributable to cis complex ap-
peared. The 31P NMR resonance for the trans complex shows a sin-
gle peak downfield from that of the cis complex. The cis to trans
isomerization process in the ruthenium species [Ru(S2-
COiPr)2(PPh3)2]0/+ was induced by the oxidation reaction, which
led to the formation of trans-[Ru(S2COiPr)2(PPh3)2]+ with d5-ruthe-
nium(III) [10]. Treatment of cis-[Ru(S2COEt)2(PPh3)2] with less
bulky PMe2Ph gave trans-[Ru(S2COEt)2(PMe2Ph)2] [16], which is
the first example of Ru(II) bis(xanthate) complex with a trans
(w), 405 (s).
leff = 1.94 lB at 296 K. Anal. Calc. for
C45H48N3O4ClP2S4Ruꢀ2(CH2Cl2): C, 47.4; H, 4.40; N, 3.53. Found:
C, 47.2; H, 4.37, N, 3.52%.
2.8. X-ray crystallography
Crystallographic data and experimental details for 1, 2,
4ꢀCH2Cl2, and 6 in Table 1 and for 7ꢀ2CH2Cl2, 8, and 9ꢀ2CH2Cl2 in
Table 2 are summarized. Intensity data were collected on a Bruker
SMART APEX 2000 CCD diffractometer using graphite-monochro-
mated Mo Ka radiation (k = 0.71073 Å) at 293(2) K. The collected
frames were processed with the software SAINT [23]. The data was
corrected for absorption using the program SADABS [24]. Structures
were solved by the direct methods and refined by full-matrix
least-squares on F2 using the SHELXTL software package [25]. All
non-hydrogen atoms were refined anisotropically. The positions
of all hydrogen atoms were generated geometrically (Csp3–H =
0.96 and Csp2–H = 0.93 Å), assigned isotropic thermal parameters,
and allowed to ride on their respective parent carbon or nitrogen
atoms before the final cycle of least-squares refinement. The
CH2Cl2 solvent molecule in 7ꢀ2CH2Cl2 was isotropically refined
without hydrogen atoms due to disorder. The four oxygen atoms
of the [ClO4]ꢁ anion in 8 were isotropically refined. One of the
CH2Cl2 solvent molecules in 9ꢀ2CH2Cl2 was isotropically refined
with hydrogen atoms.
i
geometry. The present trans-[Ru(PPh3)2(S2COR)2] (R = nPr 1, Pr 2)
complexes can be successfully isolated on the basis of thermody-
namics. This is the first synthetic route to trans-bis(xanthate) com-
plexes of ruthenium(II) by way of controlling reaction conditions.
The solid-state structures of trans-complexes 1 and 2 have been
established by X-ray crystallography, as shown in Figs. 1 and 2. The
corresponding selected bond lengths and angles are complied in
Table 3 for comparison. Both 1 and 2 crystallized in the monoclinic
system, space group P21/n, with the ruthenium atom occupying a
special position (0, 0, 0) imposing molecular centrosymmetry.
The arrangement around the ruthenium in each complex shows
the distorted octahedral coordination geometry. The two mutually
trans xanthate ligands chelate the ruthenium atom with very acute
bite angles of 71.62(4)° for 1 and 71.55(4)° for 2, which compare
well with those in trans-[Ru(S2COEt)2(PMe2Ph)2] (72.04(3)°) [16]
and trans-[Ru(S2COEt)2(PPh3)2][PF6] (73.20(10)°) [10]. The two
trans four-membered CS2Ru rings across the central ruthenium
atom are approximately planar with deviations of 0.001 Å for 1
and 0.026 Å for 2 from the least-squares plane, which induce dis-
tortions from idealized octahedral geometry. The RuII–S bond
3. Results and discussion
i
Interaction of [Ru(PPh3)3Cl2] with nPrOCS2K or PrOCS2K in THF
at room temperature for 2 h followed by recrystallization from
CH2Cl2/Et2O at ꢁ10 °C gave trans-[Ru(PPh3)2(S2COR)2] (R = nPr 1,
iPr 2) as the sole isolable products, whereas the same reactions car-
ried out in refluxing solvent afforded cis-[Ru(PPh3)2(S2COR)2]
(R = nPr 3, iPr 4) only. It appears that reaction of [Ru(PPh3)3Cl2] with
ROCS2K initially gave the kinetic products trans-[Ru(PPh3)2(S2-
COR)2], which crystallized quickly at a relatively lower tempera-
lengths in both
1 and 2 are in the range of 2.4005(10)–
2.4139(9) Å, which are comparable to those in trans-[Ru(S2-
Table 1
Crystallographic data and experimental details for trans-[Ru(S2COPr)2(PPh3)2] (1), trans-[Ru(S2COiPr)2(PPh3)2] (2), cis-[Ru(S2COiPr)2(PPh3)2]ꢀCH2Cl2 (4ꢀCH2Cl2), and
[RuH(CO)(S2COiPr)(PPh3)2] (6).
Compound
1
2
4ꢀCH2Cl2
6
Empirical formula
Formula weight
Crystal system
a (Å)
b (Å)
c (Å)
C44H44O2P2S4Ru
896.04
Monoclinic
10.4987(6)
8.8821(5)
C44H44O2P2S4Ru
896.04
Monoclinic
10.8517(10)
9.1682(8)
C45H45O2Cl2P2S4Ru
979.96
Triclinic
10.9818(1)
12.3131(2)
17.6605(2)
99.400(1)
C41H38O2P2S2Ru
789.84
Triclinic
9.1934(3)
12.3641(4)
17.5218(6)
78.870(2)
75.762(2)
74.672(2)
1844.28(11)
22.1439(12)
21.3852(19)
a
(°)
b (°)
95.995(3)
99.273(7)
94.139(1)
c
(°)
102.634(1)
2284.45(5)
V (Å3)
2053.6(2)
P21/n
2
2099.8(3)
P21/n
2
ꢀ
ꢀ
Space group
Z
P1
P1
2
2
Dcalc (g cmꢁ3
)
1.449
1.417
1.425
1.442
Temperature (K)
296(2)
924
0.700
296(2)
924
0.684
296(2)
1006
0.749
296(2)
812
0.660
F(0 0 0)
l(Mo K
a
) (mmꢁ1
)
Total reflection
Independent reflection
18 929
4684
19 197
4849
42 432
10384
25 173
8419
Rint
0.0770
0.0503, 0.1003
0.0675, 0.1182
0.995
0.0908
0.0597, 0.1158
0.0634, 0.1425
0.974
0.0427
0.0409, 0.1008
0.0551, 0.1090
1.024
0.0853
0.0554, 0.1053
0.0616, 0.1291
0.954
b
R1a, wR2 (I > 2
r(I))
R1, wR2 (all data)
GOFc
P
P
a
R1
=
||Fo| ꢁ |Fc||/ |Fo|.
P
P
P
2
2 1=2
wR2 ¼ ½ wðjF2oj ꢁ jFc2jÞ = wjF2oj ꢂ
.
b
c
GOF = [ w(|Fo| ꢁ |Fc|)2/(Nobs ꢁ Nparam)]1/2
.

F.-H. Wu et al. / Journal of Organometallic Chemistry 694 (2009) 3844–3851
3847
Table 2
Crystallographic data and experimental details for [Ru(PPh3)2(S2CNMe2)Cl2]ꢀ2CH2Cl2 (7ꢀ2CH2Cl2), [Ru(SCNMe2OCNMe2)-(S2CNMe2)(PPh3)2][ClO4] (8), and [Ru(SCNMe2SCN-
Me2)(S2CNMe2)(PPh3)2][ClO4]ꢀ2CH2Cl2 (9ꢀ2CH2Cl2).
Compound
7ꢀ2CH2Cl2
8
9ꢀ2CH2Cl2
Empirical formula
Formula weight
Crystal system
a (Å)
b (Å)
c (Å)
C41H40NCl6P2S2Ru
986.57
Monoclinic
10.3275(2)
27.5603(4)
15.5786(3)
C45H48N3O5ClP2S3Ru
1005.50
Monoclinic
10.0643(5)
19.3298(10)
24.9177(12)
C47H52N3O4Cl5P2S4Ru
1191.42
Triclinic
11.5807(3)
13.1583(3)
18.7521(4)
78.151(1)
a
(°)
b (°)
94.996(1)
101.65(1)
74.477(1)
c
(°)
82.801(1)
V (Å3)
4417.28(14)
P21/n
4
4747.6(4)
P21/c
4
2687.08(11)
ꢀ
Space group
Z
P1
2
Dcalc (g cmꢁ3
)
1.483
1.407
1.437
Temperature (K)
296(2)
2004
0.915
296(2)
2072
0.632
296(2)
1220
0.632
F(0 0 0)
l(Mo K
a
) (mmꢁ1
)
Total reflection
Independent reflection
42 434
10 112
0.0321
0.0487, 0.1247
0.0674, 0.1355
1.014
32 939
9999
0.0663
0.0571, 0.0712
0.0669, 0.0840
0.914
49 832
12 264
0.0139
0.0412, 0.1172
0.0479 0.1247
1.022
Rint
b
R1a, wR2 (I > 2
r
(I))
R1, wR2 (all data)
GOFc
P
P
a
R1
=
||Fo| ꢁ |Fc||/ |Fo|.
P
P
P
2
2 1=2
wR2 ¼ ½ wðjF2oj ꢁ jFc2jÞ = wjF2oj ꢂ
.
b
c
GOF = [ w(|Fo| ꢁ |Fc|)2/(Nobs ꢁ Nparam)]1/2
.
Fig. 1. Perspective view of trans-[Ru(S2COPr)2(PPh3)2] 1.
Fig. 2. Perspective view of trans-[Ru(S2COiPr)2(PPh3)2] 2.
COEt)2(PMe2Ph)2] (2.380(2)–2.404(2) Å) [16], but longer than the
RuIII–S bond lengths in trans-[Ru(S2COEt)2(PPh3)2][PF6] (2.361(2)–
2.373(2) Å). This difference may be taken as the difference in the
ionic radii for ruthenium(II) and ruthenium(III). The Ru–P bond
lengths (2.3557(9) Å for 1 and 2.3577(12) Å for 2) fall in the usual
range for ruthenium(II) complexes with PPh3 ligands, but slightly
longer than those in trans-[Ru(S2COEt)2(PMe2Ph)2] (2.336(2) Å)
[16] and [Ru(S2PEt2)2(PMe2Ph)2] (2.252(2)–2.261(2) Å) [17].
The solid-state structure of 4ꢀCH2Cl2 has been determined by
X-ray crystallography, as shown in Fig. 3. The corresponding selected
bond lengths and angles are listed in Table 4. Similar complexes
such as cis-[Ru(S2COEt)2(PPh3)2] [10,14], cis-[Ru(S2CNEt2)2(PPh3)2]
[7] and cis-[Ru{S2P(OEt)2}(PPh3)2] [11] with cis geometry have
been reported. The neutral molecule is mononuclear with an octa-
hedral geometry. The two PPh3 ligands bind to the ruthenium cen-
ter with the P–Ru–P angle of 103.13(3)°, and the two chelating
ꢁ
iPrOCS2 ligands coordinate with the ruthenium with small bite
angles (S–Ru–S angle of av. 71.55(3)°). The four-membered RuS2P
rings are approximately planar. Each ring contains a pair of long
and short Ru–S bonds [Ru(1)–S(2) = 2.4593(8) Å (‘‘long”) with
Ru(1)–S(1) = 2.3839(7) Å
(‘‘short”);
Ru(1)–S(3) = 2.4556(7) Å
(‘‘long”) with Ru(1)–S(4) = 2.3964(7) Å (‘‘short”)]. The Ru–S bond
lengths in 4ꢀCH2Cl2 (av. 2.4238(7) Å) is comparable to that in cis-
[Ru{S2P(OEt)2}(PPh3)2] (av. 2.424(2) Å) with chelated dithiosphate
ligands [11], but slightly longer than those in cis-[Ru(S2C-
NEt2)2(PPh3)2] (av. 2.3952(5) Å) with chelated dithiocarbamate

3848
F.-H. Wu et al. / Journal of Organometallic Chemistry 694 (2009) 3844–3851
Table 4
Selected bond lengths (Å) and angles (°) for cis-[Ru(S2COPri)2(PPh3)2]ꢀCH2Cl2
(4ꢀCH2Cl2).
Ru(1)–S(1)
Ru(1)–S(3)
Ru(1)–P(1)
2.3839(7)
2.4556(7)
2.3073(7)
Ru(1)–S(2)
Ru(1)–S(4)
Ru(1)–P(2)
2.4593(8)
2.3964(7)
2.3207(8)
S(1)–Ru(1)–S(2)
S(1)–Ru(1)–S(3)
S(3)–Ru(1)–S(2)
P(1)–Ru(1)–S(1)
P(1)–Ru(1)–S(4)
P(2)–Ru(1)–S(3)
P(1)–Ru(1)–S(3)
P(1)–Ru(1)–P(2)
71.62(3)
95.99(3)
88.28(3)
94.59(3)
96.04(3)
86.00(3)
165.22(3)
103.13(3)
S(3)–Ru(1)-S(4)
S(4)–Ru(1)–S(2)
S(1)–Ru(1)–S(4)
P(2)–Ru(1)–S(1)
P(2)–Ru(1)–S(4)
P(1)–Ru(1)–S(2)
P(2)–Ru(1)–S(2)
71.48(2)
96.68(3)
163.48(3)
95.94(3)
93.92(3)
85.30(3)
165.69(3)
ligands [7] and the trans-complexes 1 (av. 2.4072(9) Å) and 2
(av. 2.4093(12) Å). The average Ru–P bond length of 2.3140(7) Å
in 4ꢀCH2Cl2 agrees well with those in related ruthenium(II) com-
plexes with PPh3 ligands [6–17].
ꢁ
Similar to other 1,1-dithiolate ligands R2NCS2ꢁ, R2PS2 and
(RO)2PS2ꢁ, treatment of [RuHCl(CO)(PPh3)3] with an equimolar
amount of ROCS2K in THF gave [RuH(CO)(PPh3)2(S2COR)] (R = nPr
5, Pr 6) isolated as air-stable yellow crystals. The chloride in the
Fig. 3. Perspective view of cis-[Ru(S2COiPr)2(PPh3)2] 4.
i
starting ruthenium compound was substituted by an xanthate,
and one of PPh3 ligands was dissociated to make the ruthenium(II)
center of [RuH(CO)(PPh3)2(S2COR)] in an octahedral coordination
environment. The 1H NMR spectra of 5 and 6 display characteristic
hydride resonances at d 1.57 and 1.63 ppm, respectively [11,21]. By
comparison with the 31P NMR data of complexes 1–4, the 31P sig-
nals of 5 and 6 appeared as a singlet at 41.4 and 40.6 ppm, respec-
tively, indicating that small difference for the 31P signal for PPh3
groups in these complexes is observed. The C„O stretching vibra-
tion modes were found at 1935 and 1942 cmꢁ1 in the IR spectra of
5 and 6, respectively. The solid-state structure of 6 has been con-
firmed by X-ray crystallography. Fig. 4 shows a perspective view
of 6; selected bond lengths and angles are given in Table 5. The
geometry around ruthenium is pseudo-octahedral with two
trans-binding PPh3 ligands. The P–Ru–P unit is bent with an angle
Table 3
Selected bond lengths (Å) and angles (°) for trans-[Ru(S2COPrn)2(PPh3)2] (1) and trans-
[Ru(S2COPri)2(PPh3)2] (2).
2
3
Ru(1)–S(1)
Ru(1)–S(2)
Ru(1)–P(1)
2.4139(9)
2.4005(10)
2.3557(9)
2.4128(12)
2.4058(12)
2.3577(12)
S(1)–Ru(1)–S(2)
108.38(4)
71.62(4)
180.0
180.00(4)
86.35(3)
93.65(3)
88.49(3)
91.51(3)
180.00(2)
108.45(4)
71.55(4)
180.00(9)
180.00(6)
86.92(4)
93.08(4)
86.46(4)
93.54(4)
180.00(6)
S(2)–Ru(1)–S(1)#1
S(1)–Ru(1)–S(1)#1
S(2)–Ru(1)–S(2)#1
P(1)–Ru(1)–S(1)
P(1)–Ru(1)–S(1)#1
P(1)–Ru(1)–S(2)
P(1)#1–Ru(1)–S(2)
P(1)–Ru(1)–P(1)#1
ꢁ
of 169.41(4)°. The ROCS2 ligand chelates the ruthenium center
Symmetry transformations used to generate equivalent atoms: #1 ꢁ x + 2, ꢁy + 1,
ꢁz.
with an average Ru–S bond length of 2.495(1) Å and the S–Ru–S
angle of 70.14(4)°. The Ru–S bond lengths in 6 are longer than
those in complexes 1, 2, and 4ꢀCH2Cl2. The
p back-bonding from
the metal to the C„O bond leads to elongation of Ru–S bond in
6. The Ru–H bond length of 1.69(3) Å is within the range reported
for ruthenium-hydride complexes [11,21].
Reaction of [Ru(PPh3)3Cl2] with tetramethylthiuram disulfide
[Me2NCS2]2 proceeded smoothly in THF solution to afford a para-
magnetic dithiocarbamate complex [Ru(PPh3)2(S2CNMe2)Cl2]ꢀ
2CH2Cl2 (7ꢀ2CH2Cl2) in 43% yield. The reaction involved oxidation
of ruthenium(II) to ruthenium(III) by the disulfide group in
[Me2NCS2]2 [27]. Complex 7 could not be obtained from the direct
reaction of [Ru(PPh3)3Cl2] with NaS2CNMe2 in which no redox
Table 5
Selected bond lengths (Å) and angles (°) for [RuH(CO)(S2COPri)(PPh3)2] (6).
Ru(1)–S(1)
Ru(1)–P(1)
Ru(1)–C(1)
2.4638(12)
2.3547(12)
1.825(5)
Ru(1)–S(2)
Ru(1)–P(2)
Ru(1)–H(1)
2.5261(13)
2.3582(12)
1.69(3)
S(1)–Ru(1)–S(2)
P(2)–Ru(1)–S(1)
P(2)–Ru(1)–S(2)
C(1)–Ru(1)–P(2)
C(1)–Ru(1)–S(2)
P(1)–Ru(1)–H(1)
S(1)–Ru(1)–H(1)
P(1)–Ru(1)–P(2)
70.14(4)
90.08(4)
93.65(4)
89.23(15)
104.80(15)
85.1(11)
99.6(11)
169.41(4)
P(1)–Ru(1)–S(1)
P(1)–Ru(1)–S(2)
C(1)–Ru(1)–P(1)
C(1)–Ru(1)–S(1)
C(1)–Ru(1)–H(1)
P(2)–Ru(1)–H(1)
S(2)–Ru(1)–H(1)
93.00(4)
96.93(4)
88.58(15)
174.84(15)
85.4(11)
84.4(11)
169.6(11)
Fig. 4. Perspective view of [RuH(CO)(S2COiPr)(PPh3)2] 6.

F.-H. Wu et al. / Journal of Organometallic Chemistry 694 (2009) 3844–3851
3849
Table 6
Selected bond lengths (Å) and angles (°) for [Ru(PPh3)2(Me2dtc)Cl2]ꢀ2CH2Cl2
(7ꢀ2CH2Cl2).
Ru(1)–S(1)
Ru(1)–Cl(1)
Ru(1)–P(1)
2.4038(10)
2.3795(9)
2.4071(9)
Ru(1)–S(2)
Ru(1)–Cl(2)
Ru(1)–P(2)
2.3724(10)
2.3722(9)
2.4051(9)
S(2)–Ru(1)–S(1)
Cl(2)–Ru(1)–Cl(1)
Cl(2)–Ru(1)–S(1)
Cl(2)–Ru(1)–P(2)
Cl(1)–Ru(1)–P(2)
Cl(2)–Ru(1)–P(1)
Cl(1)–Ru(1)–P(1)
P(2)–Ru(1)–P(1)
71.43(3)
105.31(4)
156.30(4)
87.93(3)
90.54(3)
88.14(3)
86.96(3)
174.62(3)
Cl(2)–Ru(1)–S(2)
S(2)–Ru(1)–Cl(1)
Cl(1)–Ru(1)–S(1)
S(2)–Ru(1)–P(2)
S(1)–Ru(1)–P(2)
S(2)–Ru(1)–P(1)
S(1)–Ru(1)–P(1)
87.25(3)
166.56(4)
96.95(4)
94.75(3)
83.75(3)
88.73(3)
101.27(3)
reaction occurred. Magnetic susceptibility measurements in the
solid-state showed that 7 is paramagnetic with one unpaired elec-
tron, consistent with the trivalent state of ruthenium (low-spin d5,
S = 1/2) in this complex. The IR bands near 1500 and 1000 cmꢁ1 for
the two complexes are characteristic for the C@N (1531 cmꢁ1) and
C–S (997 cmꢁ1) stretching vibration modes of the Me2NCS2ꢁ ligand
(see Table 6).
Fig. 6. Perspective view of cation [Ru(SCNMe2OCNMe2)(S2CNMe2)(PPh3)2]+ in 8.
The molecular structure of 7ꢀ2CH2Cl2, as shown in Fig. 5, was
determined by single-crystal X-ray diffraction. Elemental analyses
indicated the ratio of complex to the cocrystallized CH2Cl2 in the
crystals is 1:2. The central ruthenium atom of 7ꢀ2CH2Cl2 is in an
octahedral coordination environment, containing one chelated
dithiocarbamate ligand, two mutually trans PPh3 ligands and two
mutually cis chlorides. The dithiocarbamate binds to ruthenium
in a S,S0-bidentate mode, forming a four-membered ring with a
S(1)–Ru(1)–S(2) bite angle of 71.43(3)°. The two Ru–S bond lengths
in 7ꢀ2CH2Cl2 are 2.404(1) and 2.372(1) Å, which compare well with
those in the ruthenium(III/IV)–dithiocarbamate complexes such as
[Ru3(S2CNEt2)6(DMSO)](I3)2 (DMSO = dimethyl sulfoxide) (av.
2.369(4) Å) [26], [Cp*Ru(S2CNMe2)2][N(PSPh2)2] (av. 2.387(1) Å)
[27], [Cp*RuCl2{S2P(OiPr)2}] (av. 2.364(1) Å) and [Cp*RuCl2(S2-
(av. 2.478(1) Å) and [CpRu(S2CNMe2)(PPh3)] (Cp =
g-C5H5)
(2.399(14) Å) [28]. The average Ru–P bond length of 2.4061(9) Å
in 7ꢀ2CH2Cl2 is similar to that in the ruthenium(III)-PPh3 complex
[Ru(PPh3)2(L)Cl2] (L = 2-hydroxy-acetophenone) (2.421(1) Å) [29],
but longer than those in the ruthenium(II)-PPh3 complexes such
as RuH(S2CNMe2)(CO)(PPh3)2 (av. 2.356(1) Å) [28], [Ru{S2-
P(OEt)2}2(PPh3)2] (av. 2.332(1) Å) and [RuH(CO){S2P(OEt)2}(PPh3)2]
(av. 2.351(1) Å) [11]. The average Ru–Cl bond length in 7ꢀ2CH2Cl2
(2.3759(9) Å) is comparable to that in the ruthenium(III) complex
[Ru(PPh3)2(L)Cl2] (L = 2-hydroxy-acetophenone) (2.371(1) Å) [29],
but shorter than that in the ruthenium(II) complex [(g
6-p-cyme-
ne)RuCl(S2CNMe2)] (2.428(1) Å) [30]. The Cl(1)–Ru(1)–Cl(2) angle
of 105.31(4)° in 7ꢀ2CH2Cl2 is normal for the cis Ru(III) dichloride
compounds.
COiPr)] (av. 2.360(1) Å) [6] (Cp* =
g-C5Me5), are slightly shorter
than those in ruthenium(II)-dithiocarbamate complexes such as
Ru(S2CNEt2)2(CO)ꢀ1/2I2 (av. 2.427(2) Å) [26], RuH(S2CNMe2)
(CO)(PPh3)2 (av. 2.473(1) Å), Ru(SiClPh2)(S2CNMe2)(CO)(PPh3)2
The chlorides in complex 7 are leaving groups that may easily be
substituted to give new compounds. Treatment of 7 with 1 equiv.
of [M(MeCN)4][ClO4] (M = Cu, Ag) gave the stable ruthenium(III)
cationic complexes [Ru{C(NMe2)QC(NMe2)S}-(S2CNMe2)(PPh3)2]
[ClO4] (Q = O 8, S 9) with ruthenium–carbon bonds. Complex 7
was converted to 8 or 9 upon treatment with the d10 Cu+ or Ag+
ion in a mixed CH2Cl2/MeCN soꢁlvent. The reaction involved the
C–S bond cleavage of Me2NCS2 to give the active [Me2NCS]ꢁ
specie and two [Me2NCS]ꢁ species dimerize to give a new ligand
[C(NMe2)SC(NMe2)S]ꢁ. Of note is the formation [CH(NMe2)OC
(NMe2)S]ꢁ due to the hydrolysis of the active [Me2NCS]ꢁ species
in a relatively long time reaction [31–33]. The measured leff values
of 1.92 lB for 8 and 1.94 lB for 9 are consistent with the ruthe-
nium(III) formulation for both two complexes. The IR spectra of
two complexes displayed a distinct m
(Cl@O) band at 1095 cmꢁ1
in the region expected for the [ClO4]ꢁ anion. The IR spectra of
ꢁ
two complexes are consistent with bidentate Me2NCS2 ligands,
the
with the cheleted CS2-bound from observed in the crystallographic
determination. The assignment the (C–O) band in 8 is more prob-
m(C@N) and m(C–S) bands are clearly resolved and consistent
m
lematic, due to overlap with other vibrations; a tentative assign-
ment at 696 cmꢁ1 as a strong peak is proposed. However, the
m
(C–S) band for C(4)–S(4) bond in the spectrum of 9 is clearly
observed at 451 cmꢁ1 as a sharp peak.
The solid-state structures of both complexes 8 and 9ꢀ2CH2Cl2
have been unambiguously confirmed by X-ray crystallography.
Figs. 6 and 7 show perspective views of 8 and 9, respectively; se-
lected bond lengths and angles of two complexes are complied in
Fig. 5. Perspective view of [Ru(PPh3)2(S2CNMe2)Cl2] 7.

3850
F.-H. Wu et al. / Journal of Organometallic Chemistry 694 (2009) 3844–3851
membered chelated metallacycles are essentially planar with devi-
ations of 0.026 Å for 8 and 0.054 Å for 9ꢀ2CH2Cl2 from the least-
squares planes defined by Ru(1), S(3), C(8), O(1) and C(6) in 8
and Ru(1), S(3), C(8), S(4) and C(6) in 9ꢀ2CH2Cl2, respectively. The
alkylcarbamate [C(NMe2)QC(NMe2)S]ꢁ ligands are planar with
C(4) lying 0.26 Å for 8 and 0.17 Å for 9ꢀ2CH2Cl2 out of the least-
squares planes, indicative of
p
donation from the sp2 carbon to
the ruthenium, which is further supported by the pattern of bond
lengths within ligands: double and single bonds between C(8) and
S(3) [1.698(5) Å for 8 and 1.686(3) Å for 9ꢀ2CH2Cl2] and O(1)/S(4)
[C(8)–O(1) = 1.410(6) Å for
8 and C(8)–S(4) = 1.722(3) Å for
9ꢀ2CH2Cl2], and considerable partial double-bond character of
C(6)–N(2) bond lengths (1.338(6) Å for 8 and 1.328(4) Å for
9ꢀ2CH2Cl2). The Ru(1)–C(6) bonds at 1.975(5) Å for
8 and
2.018(3) Å for 9ꢀ2CH2Cl2 are typical for alkyl of ruthenium(III),
which are slightly longer than those in ruthenium(II)-alkyls such
as [Ru{C(C@CPh2)SC(NMe2)S}(S2CNMe2)(CO)(PPh3)] (2.148(5) Å)
[32] and [Ru{CH(C6H4OMe)-SC(NC4H2)S}(S2CNC4H8)(CO)(PPh3)]
(2.163(5) Å) [33], but comparable to that in a ruthenium(IV) com-
plex [RuCl(S2CNMe2)(g
2-SCNMe2)] (1.996(10) Å) [31]. The Ru(1)–
S(3) dative bonds of 2.3644(14) Å in 8 or 2.3480(6) Å in 9ꢀ2CH2Cl2
are noticeably shorter than the distances between the ruthenium
and sulfur atoms of dithiocarbamate ligands, which is perhaps a
Fig. 7. Perspective view of cation [Ru(SCNMe2SCNMe2)(S2CNMe2)(PPh3)2]+ in 9.
reflection of the
p-acidity of the trans dithiocarbamate ligand.
Table 7
The Ru(1)–S(1) (trans to carbon) (2.4841(14) for 8 or 2.4979(7)
for 9ꢀ2CH2Cl2) is longer than the Ru(1)–S(2) (trans to sulfur)
(2.4087(13) for 8 or 2.4171(7) for 9ꢀ2CH2Cl2) due to trans influence
of the carbon atom. The average Ru–P bond lengths of 8 and
9ꢀ2CH2Cl2 are 2.3784(15) and 2.3874(6) Å, respectively, are slightly
shorter than those in the related trans ruthenium(III)-PPh3 com-
plexes such as 7ꢀ2CH2Cl2 (2.4061(9) Å) and [Ru(PPh3)2(L)Cl2]
(L = 2-hydroxy-acetophenone) (2.421(1) Å) [29]. The ruthenium
atoms and two phosphorus atoms are approximately collinear,
with the P–Ru–P angles deviating less than 7° from 180°.
Formal redox potentials of the ruthenium–xanthate complexes
have been determined by cyclic voltammetry. The cyclic voltam-
mograms of complexes 1–4 in CH2Cl2 show a reversible couple at
ca. 0.13–0.16 V, vs. Cp2Fe+/0, which is assigned as the metal-cen-
tered RuIII–RuII couple because [ROCS2]ꢁ ligand is redox inactive
at this potential. The RuIII–RuII for 1–4 is similar to that for cis-
[Ru(S2CNEt2)2(PPh3)2] [34]. The CV of 5 or 6 shows a reversible
RuIII–RuII couple at 0.22 V along with an irreversible oxidation
wave at 0.71 V, which is tentatively attributed to RuIII–RuIV oxida-
tion, which is similar to the electrochemical properties of the ana-
logue complex [RuH(CO){S2P(OEt)2}(PPh3)2] with dithiophosphate
ligand [11]. The cyclic voltammogram of 7 in CH2Cl2 shows two
reversible couples at ꢁ0.29 V and 0.77 V vs. Cp2Fe+/0, which are as-
signed as the metal-centered RuIII–RuII and RuIII–RuIV couples,
respectively. The one-electron nature of these responses has been
confirmed by comparing their current heights with the standard
Cp2Fe+/0 under identical experimental conditions. The metallacy-
clic complex 8 exhibits an irreversible couple at 0.28 V and a
reversible couple ꢁ1.04 V, which are assigned as the RuIV–RuIII
and RuIII–RuII couples, respectively. Similar couples at 0.29 V and
ꢁ1.09 V were observed in the cyclic voltammetry of complex 9.
The irreversibility of Ru(III/IV) oxidation for 8 and 9 suggests that
the ruthenium(III) state in these complexes is well stabilized by
Selected bond lengths (Å) and angles (°) for [Ru(SCNMe2OCNMe2)-
(S2CNMe2)(PPh3)2][ClO4]
(8)
and
[Ru(SCNMe2SCNMe2)(S2CNMe2)(PPh3)2]-
[ClO4]ꢀ2CH2Cl2 (9ꢀ2CH2Cl2).
8
9ꢀ2CH2Cl2
Ru(1)–S(1)
Ru(1)–S(2)
Ru(1)–S(3)
Ru(1)–P(1)
Ru(1)–P(2)
Ru(1)–C(6)
2.4841(14)
2.4087(13)
2.3644(14)
2.3791(15)
2.3776(15)
1.975(5)
2.4979(7)
2.4171(7)
2.3480(6)
2.3942(6)
2.3807(6)
2.018(3)
S(1)–Ru(1)–S(2)
S(1)–Ru(1)–S(3)
S(2)–Ru(1)–S(3)
P(1)–Ru(1)–S(1)
P(1)–Ru(1)–S(2)
P(1)–Ru(1)–S(3)
P(2)–Ru(1)–S(1)
P(2)–Ru(1)–S(2)
P(2)–Ru(1)–S(3)
P(1)–Ru(1)–P(2)
C(6)–Ru(1)–S(3)
C(6)–Ru(1)–P(2)
C(6)–Ru(1)–P(1)
C(6)–Ru(1)–S(2)
C(6)–Ru(1)–S(1)
70.39(5)
70.28(3)
101.32(2)
171.56(2)
93.70(2)
93.82(2)
85.66(2)
84.76(2)
92.13(2)
87.91(2)
172.96(2)
87.36(8)
90.01(7)
92.55(7)
101.09(8)
169.66(8)
102.98(5)
172.99(5)
89.06(5)
91.52(5)
85.96(5)
88.69(5)
92.19(5)
89.92(5)
174.75(5)
82.19(17)
89.98(14)
92.69(14)
104.49(17)
174.66(17)
Table 7 for comparison. 8 crystallized in the monoclinic system
with space group P21/c, while 9ꢀ2CH2Cl2 crystallized in the triclinic
ꢀ
system with space group P1. Two structures consist of mononu-
clear ruthenium complex cations and discrete [ClO4]ꢁ anions. The
[ClO4]ꢁ anions have the expected structure as well as normal dis-
tances and angles, which will not be discussed further. The geom-
etry at ruthenium in each of the complexes is pseudo-octahedral,
given the constraints of two trans chelated ligands and two trans
terminal PPh3 ligands. The geometries of the phosphine, dithiocar-
bamate, and carbamatoalkyl [C(NMe2)QC(NMe2)S]ꢁ (Q = O, S) li-
gands and the charge of [ClO4]ꢁ anion are as expected for
the combination of
gands [35]. Attempts to isolate Ru(IV)–carbene complexes by oxi-
dation of or with AgOSO2CF3 or (NH4)2Ce(NO3)6 were
unsuccessful.
r-donor phosphine and electron-rich sulfur li-
ꢁ
ruthenium(III). The Me2NCS2 ligand binds to the ruthenium cen-
8
9
ter with a small bite angle (70.39(5)° for 8 or 70.28(3)° for
9ꢀ2CH2Cl2), resulting in an approximately planar four-membered
RuS2P ring which contains a pair of long and short Ru–S bonds
(2.4841(14) and 2.4087(13) Å for 8, 2.4979(7) and 2.4171(7) Å for
9ꢀ2CH2Cl2). The principal feature of interest is the metallacyclic al-
Acknowledgements
This project was supported by the Natural Science Foundation
of China (20771003) and the Program for New Century Excellent
kyl chelate of alkylcarbamate ligand as a p-donor ligand. The five-

F.-H. Wu et al. / Journal of Organometallic Chemistry 694 (2009) 3844–3851
3851
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of Anhui Province (2006kj035a) for the assistance.
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Appendix A. Supplementary material
CCDC 719648, 719649, 719650, 719651, 719652, 719653 and
722410 contain the supplementary crystallographic data for 1, 2,
4ꢀCH2Cl2, 6, 7ꢀ2CH2Cl2, 8, and 9ꢀ2CH2Cl2. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif. Supplementary
data associated with this article can be found, in the online version,
at doi:10.1016/j.jorganchem.2009.04.026.
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