Nickel-heterocumulene complexes stabilized by trimethylphosphine: Synthesis, characterization and catalytic application in organozinc coupling with CS2

Article abstract of DOI:10.1016/j.ica.2012.09.002

The reactivity of Ni(PMe₃)₄ with CO₂, CS₂ and SCNPh was studied. Although CO₂ is structurally homologous compound with CS₂ and SCNPh, its reactivity with Ni(PMe₃)₄ shows a different result with those of CS ₂ and SCNPh. Reactions of Ni(PMe₃)₄ with carbon disulfide and phenyl isothiocyanate in THF give the tetrahedral coordinate complexes (Me₃P)₃Ni(η²-CS₂) (1) and (Me₃P)₃Ni(η²-SCNPh) (3), characterized by standard spectroscopic methods and X-ray diffraction. Nickel(0) complexes 1 and 3 are stabilized by the strong donor ligand PMe₃. In the case of CO₂, attempts to isolate the expected nickel(0) complex (Me ₃P)₃Ni(η²-CO₂) (4) proved to be unsuccessful. To further extend the utility of our nickel catalysts, the catalytic coupling of organozinc bearing different functionalities with CS ₂ was explored. With 10 mol% of 1 as the catalyst, MeZnMe, EtZnEt and PhZnBr coupled with CS₂ to form the corresponding methyl dithiocarboxylate following esterfication of the initial products.

Full text of DOI:10.1016/j.ica.2012.09.002

Inorganica Chimica Acta 394 (2013) 446–451
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Inorganica Chimica Acta
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Nickel–heterocumulene complexes stabilized by trimethylphosphine: Synthesis,
characterization and catalytic application in organozinc coupling with CS2
⇑
Ning Huang, Xiaoyan Li, Wengang Xu, Hongjian Sun
School of Chemistry and Chemical Engineering, Shandong University, Shanda Nanlu 27, 250100 Jinan, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
The reactivity of Ni(PMe3)4 with CO2, CS2 and SCNPh was studied. Although CO2 is structurally homolo-
gous compound with CS2 and SCNPh, its reactivity with Ni(PMe3)4 shows a different result with those of
CS2 and SCNPh. Reactions of Ni(PMe3)4 with carbon disulfide and phenyl isothiocyanate in THF give the
Received 19 August 2012
Accepted 3 September 2012
Available online 13 September 2012
tetrahedral coordinate complexes (Me3P)3Ni(g g
2-CS2) (1) and (Me3P)3Ni( 2-SCNPh) (3), characterized by
standard spectroscopic methods and X-ray diffraction. Nickel(0) complexes 1 and 3 are stabilized by
Keywords:
Nickel
Carbon dioxide
Carbon disulfide
Isothiocyanate
Coupling reaction
the strong donor ligand PMe3. In the case of CO2, attempts to isolate the expected nickel(0) complex (Me3-
P)3Ni(g
2-CO2) (4) proved to be unsuccessful. To further extend the utility of our nickel catalysts, the cat-
alytic coupling of organozinc bearing different functionalities with CS2 was explored. With 10 mol% of 1
as the catalyst, MeZnMe, EtZnEt and PhZnBr coupled with CS2 to form the corresponding methyl dithio-
carboxylate following esterfication of the initial products.
Ó 2012 Elsevier B.V. All rights reserved.
1. Introduction
studies on the reactivity of Ni(PMe3)4 with CO2, CS2 and SCNPh un-
der mild conditions.
The reactivity of heterocumulenes such as carbon dioxide and
carbon disulfide, which are promising sources of C1 chemistry,
with transition metal complexes has been reviewed [1–3] and
has been shown to produce a variety of chemical transformations
[4–7]. The development of practical methods for the generation
of organic compounds from carbon dioxide, an abundant and inex-
pensive source of carbon, is essential in the future management of
this greenhouse gas. Carbon disulfide and phenyl isothiocyanate
are highly reactive, and their coordination, addition, cleavage,
and insertion reactions are currently being intensively investi-
gated. The interest in the coordination chemistry of carbon disul-
fide and phenyl isothiocyanate with transition metal complexes
stems mainly from the fact that both of them are structurally re-
lated to carbon dioxide [8–11] although it is clear that these mol-
ecules exhibit different reactivity.
2. Results and discussion
2.1. Reaction of Ni(PMe3)4 with CS2
When a solution of CS2 in THF was treated with Ni(PMe3)4 in
diethyl ether, the mixture turned from light yellow to dark red
immediately and compound 1 was isolated as a red solid in the
yield of 81% upon workup, which could be crystallized from diethyl
ether at 0 °C (Eq. (1)). The 1H NMR spectrum of 1 displays only one
set of methyl groups at room temperature.
:
ð1Þ
Since Aresta isolated the first CO2 adduct (PCy3)2Ni(g
2-CO2)
[12–14], several examples of late transition-metal carbon dioxide
coordination compounds have been reported with various binding
modes [12–15]. Carbon dioxide complexes of nickel have been
extensively studied due to their involvement in catalytic transfor-
mations [16]. As part of our studies on the coordination chemistry
of Ni(PMe3)4, we are interested in the reactivity of CO2 with
Ni(PMe3)4 and seek to investigate the binding of nickel(0) with
CO2 and its congeners, CS2 and SCNPh. Herein, we report our initial
Crystals of 1 suitable for X-ray diffraction were grown from a
diethyl ether solution at ꢀ20 °C. The molecular structure of one
of two independent molecules in the unit cell of 1 is shown in
Fig. 1 and indicates a tetrahedral coordination geometry at nickel
with the
p-coordinate C@S at one vertex of the tetrahedron. 1 is
stable in air for several hours. X-ray crystallography confirmed
the molecular configuration of 1 derived from solution data. The
length of uncoordinated C–S bond is at 1.634(3) Å, while the
⇑
g
2-coordinated C1–S1 bond length is at 1.647(3) Å. The coordina-
Corresponding author. Tel.: +86 531 88361350; fax: +86 531 88564464.
E-mail address: hjsun@sdu.edu.cn (H. Sun).
tion of C–S bond makes it a little bit longer.
0020-1693/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ica.2012.09.002

N. Huang et al. / Inorganica Chimica Acta 394 (2013) 446–451
447
Fig. 1. Perspective views of the structure of 1 with H atoms omitted for clarity and thermal ellipsoids drawn at 50% probability. (1a) Side view of the skeleton of (PMe3)3Ni(g2
CS2). (1b) Top view of the same skeleton.
-
Complex 1 presents a constant primary geometry where a metal
oxidative addition reaction (Eq. (2)) to afford (Me3P)3NiI2 with the
fragment of L3M type, formed by the metal and three phosphorus
escape of ethane. This reaction has no distinct difference with
the one of Ni(PMe3)4 and MeI (Eq. (3)) [20], which indicates that
the CS2 adduct (PMe3)3Ni(
with Ni(PMe3)4 in this case.
atoms, is g
2-bonded to a C–S linkage of the heteroallene (CS2). Se-
lected bond distances and angles for compounds 1 and 3 are re-
ported in Table 1.
g
2-CS2) (1) shows a similar reactivity
Other tetra-coordinate CS2-nickel complexes were previously
disclosed [17,18]. Nevertheless, no crystallographic data for them
were provided. In the IR spectra (Nujol mull) of complex 1 the
vibrations at 1149 and 638 cmꢀ1 can be assigned to the C@S and
2.3. Reaction of Ni(PMe3)4 with SCNPh
Treating a diethyl ether solution of phenyl isothiocyanate with
C–S bonds, respectively. They are very close to 1145 (
m
C@S) and
Ni(PMe3)4 gave rise to g
2-(C,S) nickel complex 3 (Eq. (4)). Crystal-
639 (
m
C–S) cmꢀ1 reported for (dtbpe)Ni(
g
2-CS2) by Hillhouse [19].
lization at ꢀ20 °C afforded a red crystalline solid in 72% isolated
yield. Complex 3 both in the solid state and in solution is stable
(without the change of habitus and color) at room temperature
in the air for 10 min at least.
2.2. Reaction of 1 with iodomethane
.
ð2Þ
ð3Þ
:
ð4Þ
Similar to the formation of nickel complex 1, the isothiocyanate
group is also in
2-(C,S) bonding mode in complex 3, which was
g
Motivated by our results of nickel from Eq. (1), we investigated
the reaction of iodomethane with 1. 1 reacted with excess
iodomethane in THF by dissociation, undergoing an intermolecular
largely accepted in the literature [21,22], but the structural evi-
dence for this is seldom [23–26], as is shown in Fig. 2. The IR spec-
trum (Nujol Mull) exhibits a band at 1607 cmꢀ1for the C@N
stretching vibration, while the normal value for PhNCS is
1645 cmꢀ1. The rather low value for the C@N frequency is due to
significant electron transfer to the –NCS unit from the nickel atom.
This nickel atom is very electron rich because trimethylphosphine
is a strong donor ligand.
Table 1
Selected bond distances (Å) and angles (°) for 1 and 3.
Complex 1
Ni1–S1
Ni1–C1
C1–S2
S1–C1–Ni1
S2–C1–S1
P1–Ni1–S1
C1–Ni1–P3
2.2786(11)
1.856(3)
1.634(3)
80.90(14)
136.9(2)
99.56(4)
94.48(10)
Ni1–P1
C1–S1
C2–P2
S2–C1–Ni1
C1–Ni1–S1
C1–S1–Ni1
2.2183(10)
1.647(3)
1.826(3)
142.1(2)
45.54(10)
53.56(11)
2.4. Reaction of 3 with iodomethane
.
Complex 3
Ni1–S1
Ni1–P1
2.3054(7)
2.1886(8)
1.254(3)
Ni1–C1
C1–S1
1.8675(19)
1.707(2)
N1–C1
C1–Ni1–P1
P1–Ni1–S1
N1–C1–S1
148.25(6)
101.57(2)
142.23(16)
C1–Ni1–S1
C1–S1–Ni1
N1–C1–Ni1
46.85(6)
52.96(6)
137.58(16)
ð5Þ

448
N. Huang et al. / Inorganica Chimica Acta 394 (2013) 446–451
Fig. 2. Perspective views of the structure of 3 with H atoms omitted for clarity and thermal ellipsoids drawn at 50% probability. (3a) Side view of the skeleton of (PMe3)3Ni(g2
SCNPh). (3b) Top view of the same skeleton.
-
The reaction of nickel complex 3 with excess iodomethane in
THF resulted in intermolecular oxidative addition to diiodo
nickel(II) complex 2 with the escape of ethane (Eq. (5)). The
coordinated phenyl isothiocyanate was released.
center was observed for [(dtbpe)Ni]2(g2
,l-C6H6) [19] and
[MeC(CH2PPh2)3]Ni(CO2) [28], where a bidentate and tripodal
phosphine served as an oxygen acceptor, respectively.
2.6. Comparison between molecular structures of 1 and 3
2.5. Reaction of Ni(PMe3)4 with CO2
By examining the structures complexes 1 and 3, we could detect
some geometrical difference between 1 and 3. Complex 1 crystal-
lizes in P21/n space group, while compound 3 in Pbca space group.
As seen in Figs. 1b and 2b, one of the phosphorus atoms, Pl, is con-
tained in the plane defined by the Ni, C, and S atoms, which also is
the mirror plane for the skeleton of the complexes. In both struc-
tures the angles P1–Ni1–P2 (104.17(4)0 (1); 103.29(3)0 (3)) and
P1–Ni1–P3 (103.83(4)0 (1); 104.80(3)0 (3)) are smaller than
109.50 for tetrahedral geometry (sp3 orbital hybridization), while
P2–Ni1–P3 (116.94(4)0 (1); 120.49(3)0 (3)) are larger than 109.50
because the influence of the coordinated CS2 and PhNCS ligand.
The greater deviation of angle P2–Ni1–P3 (120.49(3)0) in 3 from
109.50 comparing with that of P2–Ni1–P3 (116.94(4)0 in 1 is
caused by the larger molecular size of PhNCS comparing with that
of CS2. All of the Ni–P distances in both molecules are in the normal
region.
.
ð6Þ
Surprisingly, treatment of CO2 with a cold THF solution of
Ni(PMe3)4 (Ni: CO2 = 1:1) gave rise to nickel(0) complex
Ni(PMe3)3(CO) (5) in the yield of 32%, instead of the CO2 adduct
(PMe3)3Ni(g
2-CO2) (4) (Eq. (6)). Inspired by the unexpected result,
we attempted to improve the yield of (PMe3)3Ni(CO) (4) through
raising the Ni(PMe3)4: CO2 ratio. Unfortunately, even though the
Ni(PMe3)4: CO2 ratio was increased from 1:5 to 1:1, no appreciable
change in the yield of Ni (PMe3)3(CO) (5) was observed.
We compare the geometries of compounds 1 and 3. Here, the
same P3Ni fragment is interacted with two heteroallenic molecules
that differ in the nature of the terminal groups, namely a sulfur
atom in 1 and a NPh grouping in 3. Some evident rearrangements
This result corresponds closely to that previously reported for
[(dtbpe)Ni]2(g2
,l
-C6H6) [19]. Therefore, we suggest that the
(PMe3)3Ni(
g
2-CO2) (4) is involved as an intermediate which is
unstable and is likely to decompose under such conditions
have occurred in the geometry of the P3Ni(g
2-CS) fragment in the
(Eq. (6)). Complex 5 exhibits infrared spectrum featuring a strong
m
reported by Tolman [27]. It is proposed that the CO2 ligand in 4
is reduced to CO with PMe3 serving as reductant/O atom acceptor
giving trimethylphosphine oxide, O@PMe3, which was identified
by 1H and 31P NMR. A similar reduction of CO2 to CO at a nickel
structure of 3. The symmetry of the P3Ni fragment in 1 and 3 be-
longs to Cs group. Moreover, the plane defined by the Ni, C, and S
atoms contains P1 atom in these two compounds. The three Ni–P
bonds are more asymmetrical in 3 since their lengths are different
from each other: Ni1–P2 = 2.1870(7), Ni1–P1 = 2.1886(8) and Ni1–
P3 = 2.2119(7) Å. Quite significant for the study of the interactions
(CO) band at 1900 cmꢀ1 that corresponds to that previously

N. Huang et al. / Inorganica Chimica Acta 394 (2013) 446–451
449
Table 3
between the metal fragment and the heteroallenic molecule is the
Catalytic coupling of organozinc with CS2.a
lengthening of the Ni–S distance of about 0.03 Å on going from 1 to
3. This is a clear indication of a weakened bond. In addition, the Ni–
C distance is almost unchanged.
(8)
Other structural differences that emerge from the comparison
of the two structures are as follows: (i) The C–S (coordinated) bond
lengths are 1.647(3) and 1.707(2) Å in 1 and 3, respectively. (ii) The
bending of the coordinated g
2-CS2 (S1–C1–S2 = 136.9(2)0) in 1 is
smaller than that of PhNCS (S1–C1–N1 = 142.23(16)0) in 3 (Table 1).
(iii) In both cases, the coordination to the metal affects both link-
ages that the carbon atom forms with the adjacent atom in CS2
and SCNPh molecules. In fact, these linkages are shorter in the lin-
ear free (uncoordinated) molecules C–S = 1.55 Å in CS2 [29]; C–
S = 1.578 Å, C–N = 1.205 Å in SCNR (R = p-bromophenyl) [30]. This
bond lengthening can be regarded as the bond activation (more
precisely, weakened) by coordination. (iv) In compound 3 the phe-
nyl ring attached to the nitrogen atom is not coplanar with the SCN
plane, therefore, there is no symmetric plane in 3.
Entry
RZnXb
Time (h)
Yield (%)c
1
2
3
MeZnMe
EtZnEt
PhZnBr
16
24
12
52
32
64
a
b
c
With 10 mol% of 1, 20 mol% of PMe3.
Organozinc solution in THF.
Isolated yields.
the corresponding methyl dithiocarboxylate following esterfica-
tion of the initial products.
2.7. Catalytic coupling reactions of organozinc with CS2 catalyzed by 1
3. Conclusions
Recently, Dong and coworkers reported nickel-catalyzed aryl-
and alkylzinc carboxylations [16]. Complex 1 in our experiment
has an approximately similar structure to that of Aresta’s complex,
In conclusion, the reactivity of Ni(PMe3)4 with CO2, CS2 and
SCNPh has been studied. Although CO2 is structurally homologous
compound with CS2 and SCNPh, its reactivity with Ni(PMe3)4
shows a different result with those of CS2 and SCNPh. When CS2
Ni(g
2-CO2)(PCy3)2 [12]. We were curious to know whether the
nickel complex reported here would catalyze similar reactions.
To the best of our knowledge, no method has been developed in
metal-catalyzed organozinc coupling with CS2. Herein, we at-
tempted to use nickel complex 1 as the catalyst for coupling of
organozinc with CS2.
In our case, we found that in the presence of 10 mol% of 1 the
coupling of dimethylzinc with CS2 in THF at 40 °C followed by
treatment with MeI due to the difficulties in isolation and charac-
terization of dithiocarboxylic acids (Eq. 7), produced quantitatively
methyl dithioacetate within 16 h (Table 2, entry 3). For complexes
with different nickel sources, the catalysts showed distinct cata-
lytic activity (Table 2, entries 4–6). Compared to 1, other nickel
complexes proved to be less reactive catalysts. To confirm that
the reactions were catalyzed by nickel, control experiments were
performed, and there were no significant coupling products ob-
served (Table 2, entries 1 and 2).
and SCNPh reacted with Ni(PMe3)4, complexes (PMe3)3Ni(
g
2-SCS)
(1) and (PMe3)3Ni(
g
2-SCNPh) (3) were formed. Nickel(0) com-
plexes 1 and 3 are stabilized by the strong donor ligand PMe3. In
the case of CO2, attempts to isolate the expected nickel(0) complex
(PMe3)3Ni(g
2-CO2) (4) proved to be unsuccessful. The CO2 complex
4 was thermally unstable with respect to C–O bond cleavage and
formed (PMe3)3Ni(CO) (5) and O@PMe3 (6). The reduction of CO2
to CO is interesting, and other possible reductants (O-atom accep-
tors) have not been found to effect this transformation. Attempts to
use (PMe3)3Ni(g
2-SCS) (1) as catalyst for coupling reactions of
organozinc and CS2 were successful. In view of the outstanding
performance of Ni(PMe3)4 in the activation or cleavage of C–S
and C–O bond of CS2, SCNPh and CO2, we now plan to extend this
work with the aim of producing more diverse applications for this
novel system.
To further extend the utility of our nickel catalysts, we explored
the catalytic coupling of organozinc bearing different functional-
ities with CS2 (Eq. 8). With 10 mol% of 1 as the catalyst, MeZnMe,
EtZnEt and PhZnBr (Table 3, entries 1–3) coupled with CS2 to form
4. Experimental
4.1. General experimental methods
All reactions were carried out under nitrogen or argon atmo-
sphere using standard vacuum-line techniques. Solvents were
purified by standard procedures and were freshly distilled prior
to use. Literature method was used in the preparation of tetra-
kis(trimethylphosphine)nickel(0) [31], Infrared spectra (4000–
400 cmꢀ1), as obtained from Nujol mulls between KBr disks, were
recorded on a Bruker alpha FT-IR. Melting points were recorded in
capillary tubes. 1H (300 MHz), 13C (100.56 MHz) NMR spectra were
recorded on a Bruker Avance 300 MHz spectrometer at room tem-
perature. Chemical shifts cited were referenced to TMS (1H, 13C) as
internal standard. Elemental analyses were carried out on an Ele-
mentar Vario EL III. X-ray crystallography was performed with a
Bruker Smart 1000 diffractometer.
Table 2
Catalytic coupling of dimethylzinc with CS2.a
(7)
Entry
[Ni]
Ligandb
Time (h)
Yield (%)c
1
2
3
4
5
6
None
None
(PMe3)3Ni(
(PMe3)3Ni(
Ni(COD)2
NiCl2
None
PMe3
48
48
16
12
25
65
0
0
42
52
34
16
g
g
2-CS2)
2-CS2)
PMe3
PMe3
PMe3
4.2. Synthesis of compound 1
a
Reaction conditions: MeZnMe (2.2 mmol), CS2 (2.0 mmol), and nickel complex 1
In a 100 mL round bottomed flask, CS2 (314 mg, 4.14 mmol) in
30 mL of diethyl ether was combined with Ni(PMe3)4 (500 mg,
1.38 mmol) in 30 mL of diethyl ether at 0 °C. The reaction mixture
(10 mol%) in 2.0 mL of THF at 40 °C.
b
With 20 mol% of PMe3.
c
GC-yield relative to CS2 against internal standard (n-dodecane).

450
N. Huang et al. / Inorganica Chimica Acta 394 (2013) 446–451
Table 4
changed immediately from light yellow to red and was kept at
room temperature for 24 h. During this period, some red powder
precipitated from the diethyl ether solution. After filtration, the
solvents were reduced to give a red solid, which crystallized from
diethyl ether at ꢀ20 °C. Yield: 405 mg, 81%; m.p. (dec) >120 °C.
Anal. Calc. for C10H27NiP3S2 (363.06 g/mol): C, 33.04; H, 7.44; S,
17.63. Found: C, 33.01; H, 7.48; S, 17.58%. IR (Nujol, cmꢀ1):
Crystallographic data for complexes 1 and 3.
Compound
1
3
Empirical formula
Formula weight
Cryst syst
Space group
Unit cell dimensions
a (Å)
C
10H27NiP3S2
C16H32NNiP3S
422.11
Orthorhombic
Pbca
363.06
Monoclinic
P21/n
m
(C@S), 1149 vs.;
ppm): d 1.05 (d, 2J(PH) = 4.2 Hz, PCH3). 13C NMR (75.5 MHz, C6D6,
294 K, ppm):
65.6 (s, CS2), 127.8 (s, PCH3). 31P NMR
m
(C–S), 638 vs. 1H NMR (300 MHz, C6D6, 294 K,
9.8240(16)
15.124(3)
13.127(2)
105.981(2)
1875.1(5)
4
26.53
1.286
1.492
Dark red
20883
12.818(3)
16.936(3)
20.906(4)
90
4538.3(16)
8
28.40
1.236
1.156
Red
37941
5666
0.0383
0.0329
0.0906
b (Å)
c (Å)
d
b (°)
(121.5 MHz, C6D6, 294 K): d ꢀ28.3 (s, PCH3).
V (Å3)
Z
4.3. Synthesis of compound 3
Hmax (°)
Dcalc (g cmꢀ3
)
l
(mmꢀ1
Crystal color
)
In a 100 mL round bottomed flask, SCNPh (559 mg, 4.14 mmol)
in 30 mL of diethyl ether was combined with Ni(PMe3)4 (500 mg,
1.38 mmol) in 30 mL of diethyl ether at 0 °C. The reaction mixture
changed immediately from light yellow to red and was kept at
room temperature for 24 h. During this period, some red powder
precipitated from the diethyl ether solution. After filtration, the
solvents were reduced to give a red solid, which crystallized from
diethyl ether at ꢀ20 °C. Yield: 419 mg, 72%; m.p. (dec) >115 °C.
Anal. Calc. for C16H32NNiP3S (422.11 g/mol): C, 45.4; H, 7.58; N,
3.31; S, 7.58. Found: C, 45.3; H, 7.62; N, 3.28; S, 7.60%. IR (Nujol,
No. of reflections collected
No. of unique data
Rint
R1 (I > 2
wR2 indices (all data)
3893
0.1339
0.0353
0.0657
r(I))
mixture was stirred for 3 h at 50 °C, the reaction was quenched
by the slow addition of water (2 mL), and the organic phase was
separated. The aqueous phase was extracted with pentane
(2 ꢁ 1 mL); the combined organic phases were washed copiously
with water (2 ꢁ 1 mL) to remove the tetrahydrofuran and dried
with magnesium sulfate overnight. Distillation of the pentane
through a short Vigreaux left an orange residue, which was further
purified using flash column chromatography to give corresponding
methyl dithiocarboxylate (eluted with 5 ꢁ 15% ethyl acetate in
hexanes). The isolated sample was characterized by 1H NMR anal-
ysis. 1H NMR (300 MHz, CDCl3, 294 K, ppm): methyl dithioacetate,
CH3C(=S)SCH3, d 2.62 (s, 3H), 2.86 (s, 3H) [32]; methyl dithiopropi-
onate, CH3CH2C(=S)SCH3, d 0.98 (t, 3H), 2.90 (s, 3H), 1.72 (q, 2H);
methyl dithiobenzoate, C6H5C(=S)SCH3, d 2.82 (s, 3H), 7.36–7.51
(m, 5H).
cmꢀ1): (C–S), 656 vs. 1H NMR (300 MHz, C6D6,
m(C@N), 1607 s; m
294 K, ppm): d 1.01 (d, 2J(PH) = 4.4 Hz, PCH3); d 7.01–7.94 (m, 5H,
aromatic-H). 13C NMR (75.5 MHz, C6D6, 294 K, ppm): 13C NMR
(75.5 MHz, C6D6, 294 K, ppm): d 65.6 (s, CS2), 127.8 (s, PCH3). 31P
NMR (121.5 MHz, C6D6, 294 K): d ꢀ21.5 (s, PCH3).
4.4. Reaction of Ni(PMe3)4 with CO2
A 100 mL round bottomed flask was charged with a 40 mL
diethyl ether solution of Ni(PMe3)4 (500 mg, 1.38 mmol). Gaseous
carbon dioxide (60.72 mg, 1.38 mmol) was transferred into the
THF solution of Ni(PMe3)4 in liquid nitrogen trap. The solution
was stirred for 2 h at ꢀ78 °C before being gradually warmed to
ambient temperature. During this time, the color of the solution
changed gradually from light yellow to orange and white precipi-
tate was also noted. After filtration, Ni(PMe3)3(CO) (5) and O@PMe3
(6) were obtained as indicated by 31P NMR and by comparison to
the IR spectra with those in the literature [23]. The yields of
Ni(PMe3)3(CO) (32%) and O@PMe3 (39%) were determined by 31P
NMR.
Acknowledgments
We gratefully acknowledge the support by NSF China No.
21072113 and Prof. Dr. Dieter Fenske and Dr. Olaf Fuhr (KNMF)
for X-ray crystal diffraction.
References
4.5. X-ray crystallography
[1] K.K. Pandey, Coord. Chem. Rev. 140 (1995) 37.
[2] J.A. Ibers, Chem. Soc. Rev. 11 (1982) 57.
[3] H. Werner, Coord. Chem. Rev. 43 (1982) 165.
[4] M. Aresta, A. Dibenedetto, Dalton Trans. (2007) 2975.
Intensity data were collected on a Bruker SMART diffractometer
with graphite-monochromated Mo K
a radiation (k = 0.71073 Å).
Crystallographic data for complexes 1 and 3 are summarized in
[5] T. Sakakura, J.-C. Choi, H. Yasuda, Chem. Rev. 107 (2007) 2365.
[6] J. Louie, Curr. Org. Chem. 9 (2005) 605.
Table 4. The structures were solved by direct methods and refined
[7] H. Arakawa, M. Aresta, J.N. Armor, M.A. Barteau, E.J. Beckman, A.T. Bell, J.E.
Bercaw, C. Creutz, E. Dinjus, D.A. Dixon, K. Domen, D.L. DuBois, J. Eckert, E.
Fujita, D.H. Gibson, W.A. Goddard, D.W. Goodman, J. Keller, G.J. Kubas, H.H.
Kung, J.E. Lyons, L.E. Manzer, T.J. Marks, K. Morokuma, K.M. Nicholas, R.
Periana, L. Que, J. Rostrup-Nielson, W.M.H. Sachtler, L.D. Schmidt, A. Sen, G.A.
Somorjai, P.C. Stair, B.R. Stults, W. Tumas, Chem. Rev. 101 (2001) 953.
[8] L.D. Field, E.T. Lawrenz, W.J. Shaw, P. Turner, Inorg. Chem. 39 (2000) 5632.
[9] A. Del Zotto, E. Rocchini, F. Pichierri, E. Zangrando, P. Rigo, Inorg. Chim. Acta
299 (2000) 180.
with fullmatrix least-squares on all F2
(SHELXL-97) with non-
hydrogen atoms anisotropic.
CCDC 850128 and 850129 contain the supplementary crystallo-
graphic data for 1 and 3. These data can be obtained free of
charge from The Cambridge Crystallographic Data Center via
www.ccdc.cam.ac.uk/data_request/cif.
[10] A.S. Batsanov, A.V. Churakov, J.A.K. Howard, A.K. Hughes, A.L. Johnson, A.J.
Kingsley, I.S. Neretin, K. Wade, J. Chem. Soc., Dalton Trans. 21 (1999) 3867.
[11] J. Vicente, M.T. Chicote, P. González-Herrero, P.G. Jones, Chem. Commun. 21
(1997) 2047.
4.6. Representative procedure for the Ni-catalyzed organozinc coupling
with CS2
[12] M. Aresta, C.F. Nobile, V.G. Albano, E. Forni, M. Manassero, J. Chem. Soc., Chem.
Commun. 15 (1975) 636.
Under N2 atmosphere, to a 25 mL Schlenk tube containing a
solution of 1 (72.6 mg, 0.2 mmol) in 2 mL of THF were added an
organozinc (2.2 mmol) and CS2 (152 mg, 2.0 mmol). The reaction
mixture was stirred at 40 °C until there was no CS2 left (monitored
by GC–MS). Then MeI was added to the mixture (1 mL). After the
[13] M. Aresta, C.F. Nobile, J. Chem. Soc., Dalton Trans. 7 (1977) 708.
[14] M. Aresta, R. Gobetto, E. Quaranta, I. Tommasi, Inorg. Chem. 31 (1992) 4286.
[15] C.H. Lee, D.S. Laitar, P. Mueller, J.P. Sadighi, J. Am. Chem. Soc. 129 (2007) 13802.
[16] C.S. Yeung, V.M. Dong, J. Am. Chem. Soc. 130 (2008) 7826.
[17] M.A. Bennett, J.A. Johnson, A.C. Willis, Organometallics 15 (1996) 68.

N. Huang et al. / Inorganica Chimica Acta 394 (2013) 446–451
451
[18] T. Yamamoto, T. Kohara, K. Osakada, A. Yamamoto, Bull. Chem. Soc. Jpn. 56
(1983) 2147.
[25] S. Gambarotta, M.L. Fiallo, C. Floriani, A. Chiesi-Villa, C. Guastini, Inorg. Chem.
23 (1984) 3532.
[19] J.S. Anderson, Inorg. Chem. 49 (2010) 10203.
[20] H.F. Klein, H.H. Karsch, Chem. Ber. 109 (1976) 2515.
[21] H. Werner, Coord. Chem. Rev. 43 (1982).
[22] R.O. Harris, J. Powell, A. Walker, P.V. Yaneff, J. Organomet. Chem. 141 (1977)
217.
[26] R. Flugel, O. Gevert, H. Werner, Chem. Ber. 129 (1996) 405.
[27] C.A. Tolman, J. Am. Chem. Soc. 92 (1970) 2956.
[28] C. Bianchini, D. Masi, C. Mealli, A. Meli, M. Sabat, Inorg. Chem. 23 (1984) 2731.
[29] A.H. Guenter, J. Chem. Phys. 31 (1959) 1095.
[30] L. Ulicky, Zb. Pr. Chemickotechnol. Fak. SVST 47 (1969) 288.
[31] H.-F. Klein, H.H. Karsch, Angew. Chem. 82 (1970) 885.
[32] F.L. Lu, J. Org. Chem. 54 (1989) 2165.
[23] C. Bianchini, D. Masi, C. Mealli, A. Meli, J. Organomet. Chem. 247 (1983) C29.
[24] C. Bianchini, D. Masi, C. Mealli, A. Meli, Inorg. Chem. 23 (1984) 2838.