Synthesis and reactivity of a novel hydridocobalt(III) complex containing trimethylphosphine and thiophenolato ligands

Article abstract of DOI:10.1016/j.jorganchem.2007.06.031

The novel hydridocobalt(III) complex [mer-Co(H)(SPh)₂(PMe₃)₃] (1) was prepared by reaction of thiophenol with [Co(PMe₃)₃Cl], [Co(PMe₃)₄] and [Co(PMe₃)₄Me]. A dinuclear cobalt dithiophenolato complex [Co(PMe₃)₂(SPh)]₂ (2) was obtained from the reaction of thiophenol with [Co(PMe₃)₄Me]. Reaction of 1 with iodomethane afforded complex [Co(PMe₃)₃(I)₂] (3). Reaction of complex 2 with carbon monoxide gave a mononuclear dicarbonyl cobalt(I) complex [Co(PMe₃)₃(CO)₂(SPh)] (4). The crystal structures of 1-4 were determined by X-ray diffraction. Formation mechanism of 1 is discussed.

Full text of DOI:10.1016/j.jorganchem.2007.06.031

Journal of Organometallic Chemistry 692 (2007) 4251–4258
www.elsevier.com/locate/jorganchem
Synthesis and reactivity of a novel hydridocobalt(III)
complex containing trimethylphosphine and thiophenolato ligands
*
Guili Jiao, Xiaoyan Li , Hongjian Sun, Xiaofeng Xu
School of Chemistry and Chemical Engineering, Shandong University, Shanda Nanlu 27, 250100 Jinan, People’s Republic of China
Received 23 April 2007; received in revised form 13 June 2007; accepted 19 June 2007
Available online 27 June 2007
Abstract
The novel hydridocobalt(III) complex [mer-Co(H)(SPh)2(PMe3)3] (1) was prepared by reaction of thiophenol with [Co(PMe3)3Cl],
[Co(PMe3)4] and [Co(PMe3)4Me]. A dinuclear cobalt dithiophenolato complex [Co(PMe3)2(SPh)]2 (2) was obtained from the reaction
of thiophenol with [Co(PMe3)4Me]. Reaction of 1 with iodomethane afforded complex [Co(PMe3)3(I)2] (3). Reaction of complex 2 with
carbon monoxide gave a mononuclear dicarbonyl cobalt(I) complex [Co(PMe3)3(CO)2(SPh)] (4). The crystal structures of 1–4 were deter-
mined by X-ray diffraction. Formation mechanism of 1 is discussed.
ꢀ 2007 Elsevier B.V. All rights reserved.
Keywords: Hydridocobalt(III) complex; Trimethylphosphine; Thiophenol; Crystal structure
1. Introduction
associated with several important features such as redox
behavior, unusual geometries, stabilization of uncommon
metal oxidation states, electron deficiency or abundance,
can contribute to the understanding of structure, bonding
and function of biologically important sulfur–metal sites
[7]. Polyphosphine–transition-metal complexes with bis-
sulfido coligands usually display good electron-transfer
capability [8,9]. Recently, homogeneous nickel catalysts
for the selective transfer of a single arylthio group in
the catalytic hydrothiolation of alkynes were developed
[10].
One of the difficulties in studying thiolate coordination
chemistry is that RSꢀ donors have a strong tendency to
bridge metal ions acting as bidentate soft bases. If not con-
trolled by coligands this can lead to the formation of aggre-
gates or polymers of varying size which can be hard to
study [11]. Control has been exerted by the use of bulky
substituents and/or by the use of thiolate bearing elec-
tron-withdrawing groups. Bridging of thiolates is more eas-
ily controlled with aromatic RSꢀ donors such as
thiophenolates.
Hydrido compounds of transition metals play an impor-
tant role in synthetic and industrial processes. According
to a widely accepted mechanism for the hydroformylation
process given by Heck and Breslow, a hydridocobalt com-
pound is regarded as a necessary precatalyst [1]. So far
very few examples of hydridocobalt(III) complexes are
known.
Metal thiolato complexes are known as ubiquitous bio-
logical electron-transfer mediators [2,3], yet complexes
containing both phosphine and thiolato ligands have
received relatively little attention and only a few reports
are found in this area [4]. Interest in mono- and polynu-
clear transition-metal thiolates has undergone a remark-
able increase in recent years [5]. Metal thiolate complexes
are involved in fundamental catalytic (e.g. hydrodesulfuri-
zation [6]) and biological (e.g. iron–sulfur proteins [7]) pro-
cesses. In particular, the study of sulfur–metal centers,
*
Corresponding author. Tel.: +86 531 88361350; fax: +86 531
The main purpose of this study is to investigate the reac-
tivity of the trimethylphosphine supported hydrido cobalt
88564464.
E-mail address: xli63@sdu.edu.cn (X. Li).
0022-328X/$ - see front matter ꢀ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.06.031

4252
G. Jiao et al. / Journal of Organometallic Chemistry 692 (2007) 4251–4258
SPh
Co
complex to thiophenol. At the same time some chemical
properties of the thiophenolato hydrido cobalt complexes
were studied. In this paper we report on recent studies of
the chemistry of hydridocobalt(III) complexes. In this
account reactions of thiophenol with [Co(PMe3)3Cl],
[Co(PMe3)4], and [Co(PMe3)4Me] are described. [mer-
Co(H)(SPh)2(PMe3)3] (1) could be obtained from each of
PMe3
PMe3
Et2O
HCl
Me3P
H
2 PhSH
Co(PMe ) Cl
+
3 3
ð1Þ
SPh
1
the starting materials.
A dinuclear complex [Co(P-
The molecular structure of 1 (Fig. 2) shows a hexa-coor-
dinate cobalt atom surrounded by three P-donor atoms
in a meridional configuration. Two thiophenolato donors
S1, S2 are arranged in opposite positions. The angle S2–
Co1–S1 of 177.38(4)ꢁ (Table 1) indicates the position of
the hydrogen atom. Owing to the trans-influence of the
Me3)2(SPh)]2 (2) was produced from the reaction of thiophe-
nol with [Co(PMe3)4Me]. Reaction of 1 with iodomethane
has been studied in detail. The reaction of the dinuclear com-
plex 2 with carbon monoxide afforded the mononuclear
dicarbonyl cobalt(I) complex 4. The crystal structures of
complexes 1–4 were determined by X-ray crystallography.
The formation mechanism of 1 is proposed.
˚
hydrido ligand the distance Co1–P3 (2.2726(19) A) is
˚
larger than Co1–P1 (2.2263(18) A) and Co1–P2
˚
(2.2266(19) A).
2. Results and discussion
To understand this mechanism the additional experi-
ments were carried out (Scheme 1). Lithium thiphenolate
obtained from the reaction of thiophenol with n-butylli-
thium reacted with [Co(PMe3)3Cl] directly giving rise to
dinuclear complex 2 without any evidence of formation of
the tetra-coordinate cobalt(I) intermediate (route a). This
result proves the low stability of this 16-valence-electron
cobalt(I) intermediate. The dinuclear complex 2 with the
interaction of thiophenol delivered complex 1 (route b).
Complex 1 could also be prepared through one-pot reaction
of lithium thiophenolate with [Co(PMe3)3Cl] in the presence
of thiophenol (route c).
2.1. Preparation of 1
2.1.1. Reaction of [Co(PMe3)3Cl] with thiophenol
[Co(PMe3)3Cl] reacts with thiophenol giving the novel
hydriocobalt(III) complex 1 according to Eq. (1) 1 forms yel-
low brown crystals from diethyl ether which decompose
above 80 ꢁC. In the IR spectra there is a conspicuous
m(Co–H) absorption at 1977 cmꢀ1. The 1H NMR spectrum
indicates a pattern of PMe3 signals expected for complex 1:
a virtual triplet for two trans-PMe3 groups and a doublet
for the single PMe3 ligand. A doublet of triplets appears in
2
the CoH region at ꢀ9.2 ppm with J(Pcis,H) = 111.9 Hz
and 2J(Ptrans,H) = 69.6 Hz (Fig. 1). 31P NMR data clearly
show two singlets (1:2) for three coordinated trimethylphos-
phine groups, one at ꢀ6.86 ppm for the singular PMe3 and
the other at 1.72 ppm for the two trans-PMe3 ligands.
2.1.2. Reaction of [Co(PMe3)4] with thiophenol
The reaction of [Co(PMe3)4] with thiophenol also yields
complex 1 according to Eq. (2).
Fig. 1. The NMR spectrum of the hydrido ligand of 1.
Fig. 2. Molecular structure of 1.

G. Jiao et al. / Journal of Organometallic Chemistry 692 (2007) 4251–4258
4253
Table 1
SPh
Co
The selected bond distances and angles of complexes 1–4
PMe3
PMe3
Et2O
Me3P
H
Co(PMe3)4
˚
PhSH
+
Complex
Bond distances (A)
Bond angle (ꢁ)
ð2Þ
1
Co1–P1 2.2264(17)
Co1–P2 2.2265(19)
Co1–P3 2.2701(19)
Co1–S2 2.274(2)
Co1–S1 2.2749(19)
Co1–H1 1.45(2)
P1–Co1–P2 159.41(5)
P1–Co1–P3 100.35(6)
P2–Co1–P3 100.24(5)
P1–Co1–S2 94.79(4)
P2–Co1–S2 85.57(4)
P3–Co1–S2 88.85(5)
P1–Co1–S1 85.62(4)
P2–Co1–S1 94.94(4)
P3-Co1–S1 88.58(5)
S2–Co1–S1 177.43(4)
SPh
1
2.1.3. Reaction of [Co(PMe3)4Me] with thiophenol
Reaction of [Co(PMe3)4Me] with thiophenol also gave
the hydrio cobalt(III) complex 1. In addition, a novel sul-
fur-bridged dicobalt(I) complex 2 was obtained (Eq. (3)).
2
Co1–P1 2.2077(5)
Co1–P2 2.2082(6)
Co1–S1 2.2399(5)
Co1–S1A 2.2412(6)
Co1–Co1A 2.3997(5)
S1–C1 1.7863(19)
S1–Co1A 2.2412(6)
P1–C9 1.826(2)
P1–C8 1.829(2)
P1–C7 1.834(2)
P2–C12 1.821(2)
P2–C10 1.823(2)
P2–C11 1.839(3)
P1–Co1–P2 100.37(2)
P1–Co1–S1 114.00(2)
P2–Co1–S1 103.30(2)
SPh
PMe3
PMe3
Me3P
H
CH
3
4
Co
4 PhSH
Co(PMe ) Me
3 4
3
+
P1–Co1–S1A 102.87(2)
P2–Co1–S1A 120.47(2)
S1–Co1–S1A 115.245(16)
P1–Co1–Co1A 125.99(2)
P2–Co1–Co1A 133.49(2)
S1–Co1–Co1A 57.648(17)
S1A–Co1–Co1A 57.596(15)
C1–S1–Co1 112.47(6)
PMe
5
3
SPh
1
PMe3
Me3P
Co
Co
Ph
S
S
Ph
+
C1–S1–Co1A 119.19(7)
Co1–S1–Co1A 64.757(16)
PMe3
Me3P
2
3
Co1–P2 2.227(3)
Co1–P1 2.248(2)
Co1–P3 2.263(2)
Co1–I1 2.6109(11)
Co1–I2 2.6285(12)
P2–Co1–P1 94.70(11)
P2–Co1–P3 95.33(9)
P1–Co1–P3 169.81(11)
P2–Co1–I1 117.01(8)
P1–Co1–I1 88.99(7)
P3–Co1–I1 110.38(8)
P1–Co1–I2 87.13(7)
P3–Co1–I2 87.69(7)
I1–Co1–I2 132.61(5)
ð3Þ
Complex 2 forms dark red crystals suitable for X-ray
diffraction which decomposes above 68 ꢁC and under ambi-
ent conditions are stable in the air for several minutes. H
1
NMR of complex 2 shows broad resonances with large
paramagnetic shifts. The molecular structure of 2 (Fig. 3)
belongs to C2h symmetry. Four atoms (Co1, S1A, S1,
Co1A) lie almost in one plane. Both cobalt(I) centers show
a tetrahedral configuration. The two bridging thiopheno-
lato ligands are arranged in opposite directions with respect
to the plane Co1–S1A–S1–Co1A. In contrast, the tetrahe-
dral core Co2(l-S)2 in [Co2(dppm)(SPh)4] is non-planar
[12]. Pushed by the bulky (diphenylphosphanyl)ethane
4
Co1–C14 1.747(3)
Co1–C13 1.757(3)
Co1–P2 2.1972(9)
Co1–P1 2.1978(10)
Co1–S1 2.3207(10)
C14–Co1–C13 118.88(16)
C14–Co1–P2 89.05(12)
C13–Co1–P2 92.10(12)
C13–Co1–P1 4.77(4)
C14–Co1–S1 126.86(11)
C13–Co1–S1 6.69(3)
P1–Co1–S1 88.55(3)
PMe3
Ph
S
Co
Me3P
Me3P
PMe3
nBuLi
Co(PMe ) Cl
+
PhSLi
+
3 3
PhSH
route a
PMe3
Co
Co
Ph
S
(1/2)
S
Ph
2
1
PMe3
PhSH
Me3P
route b
route c
+
SPh
PMe3
PMe3
Me3P
1) Co(PMe3)3Cl
2)
Co
PhSH
H
SPh
Scheme 1. Investigation of mechanism for Eq. (1).

4254
G. Jiao et al. / Journal of Organometallic Chemistry 692 (2007) 4251–4258
quantitatively [13]. The evolution of ethane could be veri-
fied with gas chromatography.
PMe3
SPh
I
PMe3
PMe3
2PhSMe
2PhSH
Me3P
H
CH I
4
Me P Co
2
+
3
C H
Co
3
2
+
2
6
I
PMe3
SPh
1
3
ð4Þ
The molecular structure of 3 (Fig. 4) shows that there
are three molecules in an unsymmetric unit. Bond lengths
and angles in the three molecules are approximately the
same. The cobalt atom lies in the center of a trigonal bipyr-
amid in which two iodine atoms and one P atom form an
equatorial plane, P1 and P3 are arranged in axial positions
with an angle P1–Co1–P3 (169.81(11)ꢁ).
2.3. Reaction of 2 with carbon monoxide
In a pentane solution under 1 bar of CO at 20 ꢁC, com-
plex 2 slowly transforms a dicarbonyl complex 4. The yel-
low crystals of complex 4 are quite air-stable and thermally
decompose above 117 ꢁC.
Fig. 3. Molecular structure of 2.
PMe3
PMe3
CO
Me3P
Co
Co
pentane
Ph
S
S
Ph
PhS
2
Co
4 CO
+
CO
PMe3
PMe3
Me3P
2
4
ð5Þ
The IR spectrum of 4 contains two strong absorptions
of terminal carbonyl ligands: 1969 cmꢀ1 (mCO) and
1886 cmꢀ1 (mCO). The molecular structure (Fig. 5) con-
Fig. 4. Molecular structure of 3.
ligand the bridging SPh-groups orient to the same side of
˚
the Co2S2-plane. The Co1–Co1A distance (2.3997(5) A)
˚
in 2 is shorter than that in [Co2(dppm)(SPh)4] (2.6 A).
2.2. Reaction of hydrido cobalt(III) complex 1 with
iodomethane
The hydrido cobalt(III) complex 1 reacts with iodome-
thane giving the tris(trimethylphosphine)diiodocobalt(II)
complex 3 according to Eq. (4). Complex 3 can be obtained
through the substitution reaction of tris(trimethylphos-
phine)dichlorocobalt(II) compound with sodium iodide
Fig. 5. Molecular structure of 4.

G. Jiao et al. / Journal of Organometallic Chemistry 692 (2007) 4251–4258
4255
firms the presence of two trimethylphosphine ligands in
axial positions with an angle P2–Co1–P1 of 174.77(4)ꢁ in
a trigonal bipyramidal coordination geometry.
4.1.1. Synthesis of [mer-Co(H)(SPh)2(PMe3)3] (1)
Method a: sample of [Co(PMe3)3Cl] (1.53 g,
A
4.7 mmol) in 40 mL of diethyl ether at ꢀ80 ꢁC was com-
bined with a solution of thiophenol (1.02 g, 9.2 mmol) in
20 mL of diethyl ether. The resulting mixture was warmed
up to 20 ꢁC and stirred for 3 h to give a yellow brown solu-
tion. A slight turbidity was filtered off and at ꢀ21 ꢁC the
solution afforded yellow brown crystals of 1 suitable for
X-ray diffraction (0.42 g, 36%). Method b: A sample of
[Co(PMe3)4] (1.70 g, 4.7 mmol) in 40 mL of pentane at
ꢀ80 ꢁC was combined with a solution of thiophenol
(0.51 g, 4.6 mmol) in 30 mL of pentane. The resulting mix-
ture was warmed up to 20 ꢁC to give a dark brown solu-
tion. A slight turbidity was filtered off and the solution at
4 ꢁC afforded yellow brown crystals of 1. After concentra-
tion the mother liquor at 4 ꢁC afforded yellow brown crys-
tals (0.32 g, 27%). Method c (one-pot reaction, route c,
Scheme 1): A sample of thiophenol (0.33 g, 2.98 mmol) in
20 mL of diethyl ether at ꢀ80 ꢁC was combined with a
solution of n-butyllithium (2.5 mol/L, 1.20 mL) of hexane.
After 1 h a sample of [Co(PMe3)3Cl] (0.97 g, 2.98 mmol)
and thiophenol (0.33 g, 2.98 mmol) were successively added
to the resulting mixture. The color of the solution changed
from red to brown yellow. After 2 h the reaction mixture
was filtered off and the filtrate at ꢀ20 ꢁC afforded yellow
brown crystals of 1 (0.94 g, 62%). Method d (route b,
Scheme 1): A sample of thiophenol (0.31 g, 2.80 mmol) in
20 mL of diethyl ether at ꢀ80 ꢁC was combined with a
solution of n-butyllithium (2.5 mol/L, 1.10 mL) of hexane.
After 1 h a sample of [Co(PMe3)3Cl] (0.90 g, 2.80 mmol)
was added to the resulting mixture. After 18 h a sample
of thiophenol (0.31 g, 2.8 mmol) was added to the reaction
solution. The filtrate at ꢀ20 ꢁC afforded yellow brown crys-
tals of 1 (0.75 g, 53%). Method e: A sample of [Co(PMe3)4]
3. Conclusion
Three different trimethylphosphine cobalt complexes
react with thiophenol under the similar experimental condi-
tions yielding the same hydridocobalt(III) complex 1. By
reaction with iodomethane all Co–S bonds of 1 are cleaved
forming a known iodocobalt compound. The dinuclear
cobalt complex 2 is a by-product in one of the syntheses
and with carbon monoxide is transformed to a mononu-
clear dicarbonyl cobalt(I) complex 4. Likely formation
mechanism of complex 1 can be suggested.
4. Experimental
4.1. General procedures and materials
Standard vacuum techniques were used in manipula-
tions of volatile and air sensitive materials. [Co(PMe3)3Cl]
[14], [Co(PMe3)4] and [Co(PMe3)4Me] [15] were prepared
by published procedures. Thiophenol was used as pur-
chased. Infrared spectra (4000–400 cmꢀ1), as obtained
from Nujol mulls between KBr discs, were recorded on
NICOLET 5700. 1H, 13C and 31P NMR (300, 75 and
121 MHz, respectively) spectra were recorded on Bruker
AVANCE 300 spectrometer. 13C and 31P NMR resonances
were obtained with broad-band proton decoupling. Ele-
mental analyses were carried out on Elementar Vario EL
III. Melting points were measured in capillaries sealed
under argon and are uncorrected.
Table 2
Crystallographic data for 1–4
Complex
1a
2
3
4
Formula
C
506.47
0.22 · 0.20 · 0.14
Triclinic
21H38CoP3S2
C24H46Co2P4S2
640.46
C9H27CoI2P3
540.95
C14H23CoO2P2S
376.25
0.21 · 0.20 · 0.13
Monoclinic
P2(1)
7.0213(14)
12.896(3)
9.999(2)
90
92.89(3)
90
904.2 (3)
2
1.382
1.239
27.05
Molecular weight
Crystal size (mm)
Crystal system
Space group
0.24 · 0.20 · 0.14
Monoclinic
P2(1)/c
10.0645(11)
11.5078(12)
14.6232(16)
90
104.232(2)
90
1641.7 (3)
4
0.30 · 0.25 · 0.15
Monoclinic
P2(1)/c
14.3055(6)
28.0578(11)
14.9298(6)
90
101.625 (3)
90
5869.6 (4)
12
ꢀ
P1
˚
a (A)
9.780(7)
12.173(9)
12.777(9)
79.888(11)
67.586(10)
66.455(11)
1288.7 (15)
2
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
V (A )
Z
Dc (g cmꢀ3
)
1.303
1.019
25.00
1.296
1.344
26.35
1.836
4.257
27.53
l (mmꢀ1
hmax (ꢁ)
)
Reflections measured
Unique reflections
R1 (I > 2r(I))
wR2 (all data)
a
6684
4519
0.0412
0.1023
9070
3349
0.0238
0.0675
29809
13389
0.0459
0.1200
4854
3358
0.0357
0.1072
The position of the hydrido hydrogen atom on cobalt atom was extracted from difference Fourier synthesis and refined.

4256
G. Jiao et al. / Journal of Organometallic Chemistry 692 (2007) 4251–4258
Table 3 (continued)
Table 3
Atomic coordinates (·104) and equivalent isotropic displacement param-
eters (A2 · 103) for complex 1–4 U(eq) is defined as one third of the trace
of the orthogonalized Uij tensor
x
y
z
U(eq)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
Co(1)
Co(2)
Co(3)
I(1)
I(2)
I(3)
I(4)
I(5)
I(6)
P(1)
P(2)
P(3)
8971(7)
594(3)
5646(6)
89(3)
104(3)
92(3)
99(3)
104(3)
118(4)
134(4)
148(5)
123(4)
97(3)
89(3)
106(3)
46(1)
43(1)
42(1)
107(1)
79(1)
74(1)
76(1)
85(1)
88(1)
69(1)
67(1)
56(1)
63(1)
62(1)
57(1)
60(1)
72(1)
64(1)
100(3)
135(3)
135(3)
10132(5)
9242(6)
6430(7)
5843(6)
7756(7)
4873(6)
6134(9)
5608(7)
8149(7)
7465(6)
9233(6)
2609(1)
7699(1)
7297(1)
4189(1)
2261(1)
6659(1)
8679(1)
7455(1)
8640(1)
2765(2)
1250(1)
2668(1)
7745(2)
6402(1)
8984(1)
7993(1)
6017(2)
6810(1)
6486(7)
7331(8)
6971(8)
1297(3)
568(3)
6700(7)
7558(6)
3588(5)
2390(7)
3305(7)
1365(8)
1958(8)
116(7)
x
y
z
U(eq)
171(3)
Complex 1
Co(1)
P(1)
P(2)
P(3)
S(1)
S(2)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(190)
C(200)
C(210)
ꢀ606(3)
ꢀ542(4)
427(4)
1210(4)
963(4)
3253(1)
4458(1)
2863(1)
932(1)
7500(1)
7749(1)
7249(1)
7500(1)
9537(1)
5464(1)
7500(1)
5655(1)
9347(1)
7500(1)
7534(1)
7465(1)
7911(3)
8155(3)
8492(4)
8573(4)
8317(4)
7999(3)
7085(3)
7005(3)
6682(4)
6422(4)
6507(4)
6851(3)
4792(3)
4765(3)
5377(3)
9623(3)
34(1)
42(1)
42(1)
65(1)
43(1)
43(1)
40(1)
53(1)
68(1)
78(2)
71(1)
54(1)
41(1)
51(1)
70(1)
76(2)
69(1)
53(1)
57(1)
60(1)
53(1)
54(1)
57(1)
61(1)
88(3)
71(3)
109(4)
107(4)
87(3)
69(3)
2166(1)
4237(1)
3126(4)
4514(5)
5128(5)
4390(7)
3038(6)
2403(5)
6310(4)
6898(5)
8508(6)
9556(5)
9008(5)
7387(4)
3319(5)
5569(5)
5955(4)
4718(4)
1879(4)
1792(5)
1211(3)
457(3)
544(6)
ꢀ724(5)
10267(3)
9717(4)
10385(5)
11597(5)
12150(4)
11498(4)
4732(3)
3507(4)
2856(4)
3410(5)
4617(5)
5285(4)
8759(4)
6451(4)
8391(4)
6616(4)
6238(4)
8550(4)
8957(8)
6616(8)
7098(11)
7900(11)
6046(7)
8368(8)
365(4)
553(7)
1868(1)
1448(1)
227(1)
1956(1)
1750(1)
662(1)
1844(1)
ꢀ593(1)
624(1)
1071(1)
1892(1)
2661(1)
1840(1)
1835(1)
995(1)
3569(1)
6653(1)
1541(1)
2964(1)
5218(1)
6432(1)
8160(1)
740(1)
2806(1)
3511(2)
2538(2)
3847(1)
5366(1)
6922(1)
6610(1)
489(1)
P(4)
P(5)
P(6)
P(7)
P(8)
P(9)
C(10)
C(13)
C(14)
10200(3)
10232(3)
6977(9)
6294(7)
8588(8)
6410(8)
8027(9)
8709(7)
566(1)
691(1)
1235(2)
2683(1)
7115(7)
5169(8)
4389(8)
ꢀ332(10)
1266(10)
ꢀ519(11)
183(13)
599(11)
ꢀ826(8)
ꢀ169(1)
2483(3)
2434(3)
1563(4)
Complex 4
Co(1)
P(2)
P(1)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
1868(1)
1041(1)
2727(1)
2673(4)
4627(4)
5946(4)
5367(5)
3422(6)
2087(5)
4583(6)
3683(6)
791(6)
2030(1)
3652(1)
395(1)
7537(1)
7163(1)
7714(1)
4162(3)
4496(3)
3515(3)
2162(4)
1819(3)
2799(3)
6636(5)
9373(4)
7394(5)
8656(5)
6002(5)
6524(4)
8682(4)
8135(3)
5323(1)
9557(4)
8649(3)
25(1)
29(1)
30(1)
29(1)
31(1)
34(1)
38(1)
40(1)
35(1)
43(1)
44(1)
43(1)
51(1)
40(1)
40(1)
37(1)
31(1)
31(1)
62(1)
45(1)
Complex 2
Co(1)
S(1)
P(1)
P(2)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
4743(1)
5555(1)
6090(1)
3027(1)
7245(2)
8358(2)
9661(2)
9854(3)
8748(3)
7456(2)
7904(2)
6269(3)
5656(3)
3396(2)
2196(3)
1547(3)
4082(1)
5591(1)
2540(1)
3448(1)
5337(2)
5985(2)
5776(3)
4937(3)
4311(2)
4510(2)
2797(2)
1586(2)
1479(2)
3338(2)
2038(2)
4411(3)
305(1)
1243(1)
549(1)
30(1)
35(1)
40(1)
40(1)
38(1)
52(1)
70(1)
74(1)
72(1)
56(1)
71(1)
63(1)
77(1)
62(1)
77(1)
77(1)
1925(2)
2018(3)
2102(3)
2140(3)
2089(3)
1981(3)
ꢀ32(3)
21(3)
ꢀ524(3)
4461(4)
4341(3)
3883(3)
1837(3)
2459(3)
1714(1)
1710(3)
2761(2)
864(1)
1955(1)
1852(2)
2433(2)
3112(2)
3237(2)
2661(2)
596(2)
1572(2)
ꢀ406(2)
2146(2)
514(2)
C(10)
C(11)
C(12)
C(13)
C(14)
S(1)
1229(8)
2495(5)
ꢀ1374(5)
84(5)
4113(4)
892(1)
C(9)
C(10)
C(11)
C(12)
663(2)
Complex 3
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
O(1)
O(2)
ꢀ924(4)
3777(6)
2980(9)
1804(6)
1000(7)
205(6)
851(3)
790(3)
698(3)
4337(7)
2470(7)
3751(6)
1630(7)
3047(7)
1830(7)
2981(6)
4203(6)
4786(6)
6124(7)
7982(5)
4819(9)
99(3)
127(4)
91(3)
115(3)
103(3)
116(4)
82(2)
84(2)
95(3)
116(4)
81(2)
179(7)
5517(4)
1449(3)
1852(3)
2427(3)
3072(3)
2932(3)
2814(3)
1792(4)
1641(3)
1815(5)
(1.68 g, 4.4 mmol) in 30 mL of diethyl ether at ꢀ80 ꢁC was
combined with a solution of thiophenol (0.5 g, 4.5 mmol)
in 20 mL of diethyl ether under vigorous stirring to give
a red brown mixture which was kept stirring for 15 h at
20 ꢁC. All volatile materials were removed in vacuo. The
residue was extracted with 50 mL of pentane. Crystallisa-
tion at 4 ꢁC afforded yellow brown crystals of 1 suitable
for X-ray diffraction (0.28 g, 13%). M.p.: 80 – 80.4 ꢁC,
983(7)
2908(6)
1632(6)
3631(6)
5295(6)
6086(5)
8755(9)
C(9)
C(11)
C(12)
C(15)

G. Jiao et al. / Journal of Organometallic Chemistry 692 (2007) 4251–4258
4257
Anal. Calc. for C21H38CoP3S2, (506.47 g/mol): C, 49.80, H,
7.56; Found: C, 50.21, H, 7.25%. IR(nujol, cmꢀ1): 1975 s
cmꢀ1): 1969, 1886 (CO), 1572 (C@C).1H NMR
(300 MHz, CDCl3, 297 K) d 1.51 (d, 2J(PH) = 4.2 Hz,
18H, PCH3), 6.82 (t, 3J = 14.4 Hz, 1H, CH), 7.00 (t,
(Co-H), 1573
s
(C@C).1H NMR (300 MHz, C6D6,
2
3
297 K): d 1.13 (d, J(PH) = 7.2 Hz, 9H, PCH3), 1.22 (t,
3J = 15.0 Hz, 2H, CH), 7.35 (d, J = 9.9 Hz, 2 H, CH);
2
j J(PH) + 4J(PH)j = 7.2 Hz, 18 H, PCH3), 6.91(t,
31P NMR (121 MHz, CDCl3, 297 K): d ꢀ26.46.
3J = 14.4 Hz, 2 H, CH), 7.12 (t, J = 16.2 Hz, 4 H, CH),
3
8.20 (d, 3J = 7.2 Hz,
4
H, CH). ꢀ9.22 (dt, 2J
4.4. X-ray structure determination
(PtransH) = 111.9 Hz, 2J (PcisH) = 69.6 Hz, CoH); 13C
NMR (75 MHz, C6D6, 297 K): d 14.88 (d, 1J(PC) = 21 Hz,
PCH3), 17.86 (t, | 1J(PC) + 3J(PC) | = 29.2 Hz, PCH3),
120.2, 129.6, 146.7, 146.8. 31P NMR (121 MHz, C6D6,
297 K): d ꢀ6.86 (s, 1P), 1.72 (s, 2P).
The crystal structure data for 1–4 are summarized in
Table 2. Table 3 shows the atomic coordinates of complex
1–4. X-ray data were collected on a Bruker Smart APEX
CCD area detector diffractometer (graphite-monochro-
˚
mated Mo Ka radiation, k = 0.71073 A). The structures
4.1.2. Synthesis of [Co(PMe3)2(SPh)]2 (2)
were solved by direct methods and refined with full-matrix
least-squares on all F2 (SHELXL-97) with non-hydrogen
atoms anisotropic.
Method a (route a, Scheme 1): A sample of thiophenol
(0.16 g, 1.40 mmol) in 20 mL of diethyl ether at ꢀ80 ꢁC
was combined with a solution of n-butyllithium (2.5 mol/
L, 0.60 mL) of hexane. After 1 h a sample of [Co(P-
Me3)3Cl] (0.58 g, 1.8 mmol) added to the resulting mixture.
The reaction solution was warmed up to the room temper-
ature to give a red solution. All of the volatiles were
removed in vacuo. The residue was extracted with 30 mL
of pentane. Crystallization at ꢀ20 ꢁC afforded dark red
crystals of 2 (0.30 g, 67%). Method b: A sample of [Co(P-
Me3)4Me] (1.68 g, 4.4 mmol) in 30 mL of diethyl ether at
ꢀ80 ꢁC was combined with a solution of thiophenol
(0.5 g, 4.5 mmol) in 20 mL of diethyl ether under vigorous
stirring to give a red brown mixture which was kept stirring
for 15 h at 20 ꢁC. All volatile materials were removed in
vacuo. The residue was extracted with 50 mL of pentane.
After complex 1 had been collected at 4 ꢁC crystallization
of the mother liquor at ꢀ21 ꢁC afforded dark red crystals
of 2 suitable for X-ray diffraction (0.26 g, 20%). M.p.:
>68 ꢁC (dec.). Anal. Calc. for C24H46Co2P4S2, (640.46 g/
mol): C, 45.00; H, 7.24. Found: C, 44.85; H. 7.29%. IR(nu-
jol, cmꢀ1): 1570s (C@C).
Acknowledgements
We gratefully acknowledge support by NSFC No.
20572062, the Doctoral Program of MOE No.
20050422010 and 20050422011 and Shandong Scientific
Plan No. 032090105, Natural Science Foundation of Shan-
dong Y2006B18, as well as cordially thank Prof. Dr. Dieter
Fenske (Technische Universita¨t Karlsruhe, Germany) for
the crystal structure determination.
Appendix A. Supplementary material
CCDC 631271, 631272, 631273 and 631274 contain the
supplementary crystallographic data for 1, 2, 3 and 4.
These data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or
e-mail: deposit@ccdc.cam.ac.uk. Supplementary data asso-
ciated with this article can be found, in the online version,
at doi:10.1016/j.jorganchem.2007.06.031.
4.2. Reaction of 1 with iodomethane
A sample of complex 1 (0.36 g, 0.7 mmol) in 20 mL of
diethyl ether at ꢀ80 ꢁC was combined with a solution of
CH3I (0.2 g, 1.4 mmol) in 10 mL of diethyl ether under vig-
orous stirring to give a violet solution which was kept stir-
ring for 15 h at 20 ꢁC. All volatile materials were removed
in vacuo. The residue was extracted with 30 mL of pentane.
Crystallisation at ꢀ21 ꢁC afforded violet crystals of 3 suit-
able for X-ray diffraction (0.25 g, 75%).
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