Synthesis and characterization of novel nickel(II) complexes bearing N,P ligands and their catalytic activity in ethylene oligomerization

Article abstract of DOI:10.1039/b203738f

The novel chloro(1-naphthyl)[8-(diphenylphosphino)quinoline]nickel(II) (1), chloro(1-naphthyl)[2-methyl-8-(diphenylphosphino)quinoline]nickel(II) (2), and [2-methyl-8-(diphenylphosphino)quinoline]nickel(II) dichloride (3) complexes were synthesized in satisfactory yield and fully characterized. The structures of complexes 1 and 3 were determined by single crystal X-ray analysis, which indicated that complex 1 exists in a square planar configuration, while complex 3 is dimeric square pyramidal. In the presence of MAO cocatalyst, complexes 1-3 displayed good catalytic activities for ethylene oligomerization in toluene, up to 2.45 × 10⁵ g ethylene (mol Ni·h·atm)^-1 by complex 3.

Full text of DOI:10.1039/b203738f

View Article Online / Journal Homepage / Table of Contents for this issue
Synthesis and characterization of novel nickel(II) complexes bearing
N,P ligands and their catalytic activity in ethylene oligomerization
Wen-Hua Sun,*a Zilong Li,a Huaiming Hu,a Biao Wu,a Haijian Yang,a Ning Zhu,a
Xuebing Lengb and Honggen Wangb
a
State Key Laboratory of Engineering Plastics and The Center for Molecular Sciences,
Institute of Chemistry, The Chinese Academy of Sciences, Beijing 100080, China.
E-mail: whsun@infoc3.icas.ac.cn; Fax: +86 10 6255 9373; Tel: +86 10 6255 7955
State Key Laboratory of Functional Polymer, Nankai University, Tianjin 300071, China
b
Received (in Montpellier, France) 17th April 2002, Accepted 20th June 2002
First published as an Advance Article on the web 16th September 2002
The novel chloro(1-naphthyl)[8-(diphenylphosphino)quinoline]nickel(II) (1), chloro(1-naphthyl)[2-methyl-8-
(diphenylphosphino)quinoline]nickel(II) (2), and [2-methyl-8-(diphenylphosphino)quinoline]nickel(II) dichloride
(3) complexes were synthesized in satisfactory yield and fully characterized. The structures of complexes 1 and 3
were determined by single crystal X-ray analysis, which indicated that complex 1 exists in a square planar
configuration, while complex 3 is dimeric square pyramidal. In the presence of MAO cocatalyst, complexes 1–3
displayed good catalytic activities for ethylene oligomerization in toluene, up to 2.45 ꢀ 105 g ethylene
(mol Niꢁhꢁatm)ꢂ1 by complex 3.
The electron-donating roles of nitrogen, oxygen and phos-
phorus in hetero-organic compounds make such species good
ligands for transition metals.1 Bidentate ligands containing
these donor atoms are of great importance in organometallic
chemistry for their wide application in chemical industry and
material science. Representative of these achievements, the
highly active transition metal based precursors for ethylene oli-
gomerization, neutral nickel(II) complexes with chelating P,O
ligands, are successfully used in the Shell Higher Olefin Process
(SHOP)2 to produce linear a-olefins. Recently, the catalytic
properties of late transition metal complexes containing
N^N,3 N^O,4 N^P,5 O^P,5a,6 P^P7 or N^N^N8 ligands have
been considerably investigated for ethylene polymerization or
oligomerization. These works have demonstrated that the
ligands architecture plays a crucial role in adapting the activity
of the coordinated metal center. It is generally considered that
ethylene oligomerization catalyzed by the family of transition
metal complexes, the activity and selectivity are strongly
dependent on the coordination environment around the metal
center.6b Therefore, our interests focus on designing efficient
chelating N^P ligands to modify the environment around the
nickel center on the basis of their special electronic and steric
effects as mixed-donor ligands.1 Herein we report the initial
Scheme 1
results of our studies on ethylene oligomerization catalyzed
by novel nickel-based catalysts that incorporate quinolyl and
diphenylphosphinyl moieties in a single ligand.
ethylene oligomerization or polymerization. However,
attempts to prepare mono-bidentate LNiX2 type complex
failed when using ligand a with either NiCl2 or (Ph3P)2NiCl2
11
in various solvents. This may be attributed to the minimal
steric bulk of ligand a, which favors the formation of a six-
coordinated nickel(II) complex with two bidentate ligands.
On the other hand, the two small chloride ligands on the metal
center are also unfavorable for the formation of four-coordi-
nated complexes. Accordingly, it is expected to obtain mono-
bidentate nickel(II) species with a low coordination number
by increasing the steric hindrance either of the bidentate ligand
or of the metal center with other bulky ligands.
To pursue the latter strategy we introduced a bulky ligand,
naphthyl, onto the nickel center. trans-Chloro(1-naphthyl)
bis(triphenylphosphine)nickel(II)12 was employed to react with
ligand a, giving the deep yellow nickel(II) complex 1 in high
Results and discussion
Synthesis of complexes
The preparation of 8-(diphenylphosphino) quinoline (a) was
reported along with its reaction with NiX2 to form the six-
coordinated L2NiX2 type bis[8-(diphenylphosphino)quinoli-
ne]Ni(II) dihalide b9 (Scheme 1). It was found that the complex
was sensitive to air in solution due to insertion of oxygen into
the phosphorus–nickel bond with oxidation of P(III) to P(V).10
Neither of these compounds showed catalytic activity for
1474
New J. Chem., 2002, 26, 1474–1478
DOI: 10.1039/b203738f
This journal is # The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2002

View Article Online
Scheme 2
by the bidentate N^P ligand to form the corresponding
intermediate A. When R ¼ naphthyl, the quinonyl nitrogen
replaced another PPh3 , due to the steric bulk of the naphthyl,
that is intramolecular substitution, to give the bidentate chelat-
ing complex 1. In addition, the naphthyl prefers to locate cis to
the phosphine ligand due to the p-p stacking between the phe-
nyl and naphthyl rings. However, when R ¼ Cl and the ligand
was f, intermediate A underwent intermolecular substitution to
form B, and rearrangement gave the dimeric square pyramidal
complex 3.
Fig. 1 Molecular structure of complex 1.
yield. Complex 1 was very sensitive to air in solution and even
gradually decomposed during storage. Recrystallization from
CH2Cl2–hexane gave red-purple crystals suitable for X-ray dif-
fraction. It was confirmed that the ML complex crystallized in
a distorted square planar geometry (see Fig. 1).
Crystal structure of complexes 1 and 3
For the purpose of increasing the ligand dimension, 2-
methyl-8-(diphenylphosphino)quinoline (f), a derivative of
ligand a, was selected as a bidentate ligand, bearing an addi-
tion methyl group on the quinoline ring. After many efforts,
ligand f was synthesized, and reacted with trans-chloro(1-
naphthyl)bis(triphenylphosphine)nickel(II) to give the deep
red powder of complex 2 in high yield, which was characterized
by IR, 1H NMR and elemental analysis. It is stable in the solid
state but unstable in solution.
The reaction of ligand f with (Ph3P)2NiCl2 or NiCl2 gave the
stable light green nickel(II) complex 3 in high yield, but the for-
mer proceeded more easily because of the higher solubility of
(Ph3P)2NiCl2 in CH2Cl2 solvent. Characterization of complex
3 was difficult because of its poor solubility in organic solvents,
and NMR spectroscopic analysis was not possible due to its
paramagnetism. Fortunately, crystals of 3 suitable for X-ray
analysis were obtained by recrystallization from CH2Cl2 .
On the basis of the structures of 1 and 3 (see Fig. 2), the
complexation reaction would likely take the following pathway
(Scheme 2). One PPh3 on the nickel substrate was substituted
The crystallographic structure illustrates that complex 1 has a
four-coordinated, distorted square planar geometry around
the nickel center. Its molecular structure is shown in Fig. 1.
The naphthyl and diphenylphosphino groups are located in
cis position, and no trans isomer could be found (Scheme 3).
˚
The Ni–N distance 2.010 A is a little longer by 0.037, 0.036
˚
and 0.089 A, and the Ni–P distance (2.107 A) is a little shorter
˚
˚
by 0.062, 0.012 and 0.086 A than those of the known structures
of complex c13 {cis-[Ni(edmp)2]Cl2 (edmp ¼ Me2PCH2CH2
5b
˚
˚
NH2, Scheme 1), mean Ni–N 1.973 A, Ni–P 2.169 A}, complex
˚
d5a (Ni–N 1.974 A, Ni–P 2.119 A), and complex e (Ni–N
˚
˚
1.921 A, Ni–P 2.193 A), respectively. However, the Ni–Cl dis-
˚
˚
˚
tance (2.211 A) is significantly shorter, by 0.63 A, than that in c
˚
(mean Ni–Cl 2.841 A). On the other hand, the N–Ni–P angle
(87.69ꢃ) is larger by 1.5ꢃ, 2.07ꢃ and 13.8ꢃ than those of c (mean
86.2ꢃ), d (85.62ꢃ) and e (73.9ꢃ), respectively. Probably, since
the quinolyl and phosphorus form a conjugated system, the
phosphorus becomes electron rich and attracts the adjacent
nickel closer, which consequently extends the Ni–N distance
and N–Ni–P angle. Selected bond lengths and angles are listed
in Table 1.
Fig. 2 Molecular structure of complex 3.
Scheme 3
New J. Chem., 2002, 26, 1474–1478
1475

View Article Online
˚
Table 1 Selected bond lengths (A) and angles (degree) for complex 1
merization increases with increasing MAO : Ni molar ratio.
Additionally, the activity reaches as high as 2.45 ꢀ 105
g
Ni(1)–P(1)
Ni(1)–N(1)
2.1071(15) Ni(1)–Cl(1)
2.2113(15)
1.903(5)
C(31)–Ni(1)–N(1) 174.01(19)
C2H4 (mol Niꢁhꢁatm)ꢂ1 at 50 ꢃC with a 500 MAO/Ni ratio,
but the selectivity for a-olefin decreases as the temperature
increases.
2.010(4)
87.69(13)
94.81(13)
Ni(1)–C(31)
N(1)–Ni(1)–P(1)
N(1)–Ni(1)–Cl(1)
P(1)–Ni(1)–Cl(1)
P(1)–Ni(1)–C(31)
172.97(6)
87.38(14)
C(31)–Ni(1)–Cl(1) 90.49(14)
Experimental
Different from 1, complex 3 in the solid state is a centro-
symmetric dimer bridged by two chlorine atoms, Cl(1) and
Cl(1)i (symmetry code i: ꢂx, ꢂy, ꢂz) as shown in Fig. 2. Each
nickel is coordinated in a square pyramidal environment by
nitrogen and phosphorus atoms of ligand f and two bridging
chlorine atoms, and a terminal chlorine atom at the apical
Materials and physical measurements
All operations were performed in Schlenk tubes under nitro-
gen, using vacuum-line techniques. The solvents were purified
and dried under nitrogen by conventional methods. The 1H
and 13C NMR spectra were recorded at 300 MHz on a Brucker
dmx300 spectrometer at room temperature, using SiMe4 as
internal standard. IR spectra were recorded on a Perkin Elmer
2000 FI-IR instrument. Microanalyses were obtained from a
Carlo Erba 1106. The oligomerization products of ethylene
were analyzed by gas chromatography with a Beifen 3400
instrument on a SE-54 column (methylsilicone, diameter
0.32 mm, length 25 m) using a temperature program from
35–250 ꢃC. 8-Chloroquinoline (Acros), MAO (methylalumin-
oxane, Aybemarle Co., 1.4 M) and high purity ethylene
(Beijing Yanshan Petrochemical Co.) were used as received.
2-Methyl-8-chloroquinoline14 and Ph2PLi15 were prepared
according to the published methods.
˚
position. The Ni–N distance (2.093 A) is a little longer by
˚
0.12, 0.119 and 0.172 A, but contrary to 1, the Ni–P distance
˚
˚
(2.287 A) is also longer by 0.118, 0.167 and 0.094 A than those
in c, d and e, respectively. Unlike that of complex 1, the N–Ni–
P angle (84.48ꢃ) is smaller by 1.72ꢃ and 1.14ꢃ than those of c
and d, respectively. Moreover, the Ni(1)–N(1) distance is
˚
˚
longer by 0.083 A, the Ni(1)–P(1) distance longer by 0.179 A
˚
and the Ni–Cl average distance longer by 0.142 A, than those
of complex 1, while the N–Ni–P angle is less (3.21ꢃ). This phe-
nomenon indicates that there may be some repulsive inter-
action between the two closely located ligands, especially
between the 2-methyl group of quinoline ring and the P-phenyl
group in another ligand, which enables the bridged structure of
complex 3 to slightly stretch along the Ni–Ni axis, and thus
extends the relevant bond distances and angles. Selected bond
lengths and angles are listed in Table 2.
Synthesis
2-Methyl-8-(diphenylphosphino)quinoline (f). A solution of 2-
methyl-8-chloroquinoline (1.77 g, 10 mmol) in THF (10 mL)
was added dropwise to a solution of Ph2PLi (1.92 g, 10 mmol)
in THF (30 mL) at ꢂ78 ꢃC. The mixture was stirred for 1 h,
then the reaction mixture was gradually warmed up to room
temperature and allowed to stand for 24 h. After the volatiles
were removed in vacuum, 20 mL of water was added. The
resultant solution was extracted by diethyl ether (3 ꢀ 20 mL).
The combined organic layer was concentrated to about 10 mL
and hexane (30 mL) was added to deposit f as a white powder
(2.62 g, 80%), mp 168 ꢃC. Found: C, 80.84; H, 5.58; N,
4.17. C22H18NP requires C, 80.72; H, 5.54; N, 4.28%. MS (EI):
m/z 327 (M+, 100%), 250 ([M ꢂ Ph]+, 56). IR (KBr):
n/cmꢂ1 3055.5(s), 2999.9(m), 2957.4(w), 2915.5(m), 2856.0(w),
1951.3(w), 1885.2(w), 1823.9(w), 1769.8(w), 1675.0(w),
1601.1(vs),552.6(w),1496.2(s),1478.8(m),1429.9(vs),1370.3(m),
1312.8(s), 1274.2(w), 244.6(m), 1205.3(w), 1181.4(w), 1141.0(m),
1094.3(m), 1069.3(m), 1025.5(m), 1000.3(w), 976.4(w), 915.5(w),
833.7(s), 797.0(m), 763.3(m), 745.9(vs), 698.1(vs), 660.6(m),
549.6(m), 499.8(s), 472.0(m), 444.3(m), 399.2(m). 1H NMR-
(CDCl3): d 2.49 (3H, s, CH3), 6.98 (1H, m), 7.14–7.28 (12H,
m), 7.66 (1H, d, quinolyl-5-H), 7.93 (1H, d, quinolyl-4-H).
13C NMR(CDCl3): d 25.2 (CH3), 122.0 (quinolyl-3-C), 125.4
(quinolyl-6-C), 125.7 (quinolyl-10-C), 128.0, 128.1, 128.3,
133.7, 133.9, 134.1, 135.8 (quinolyl-8-C), 137.5 [P–C (of Ph)],
137.7 (quinolyl-9-C), 158.2 (quinolyl-2-C).
Ethylene oligomerization
The ethylene oligomerization catalytic behavior of complexes
1–3 was investigated using an excess of MAO as the cocatalyst
in toluene. As shown in Table 3, complex 1 shows moderate
activity [(0.13–2.05) ꢀ 105 g C2H4 (mol Niꢁhꢁatm)ꢂ1] for ethy-
lene oligomerization at 25 ꢃC, while the six-coordinated ML2
type b9 displays no activity under similar conditions, which
may be due to the electron deficiency of the four-coordinate
nickel(II). This result provides an effective way to obtain an
active center through altering the electronic and steric environ-
ment around the nickel cation. The products are mainly C4
and C6 olefins, and the selectivity to 1-C4 is very high while
appreciably lower for 1-C6 . Moreover, lower reaction tem-
peratures seem to increase the catalytic activity, giving activ-
ities up to 2.05 ꢀ 105 g C2H4 (mol Niꢁhꢁatm)ꢂ1 at 0 ꢃC for 1.
However, even lower temperatures limit the formation of the
active species, and thus decrease the activity to some extent.
On the other hand, the activity significantly decreases at tem-
peratures above 80 ꢃC, which may be caused by the decrease
of ethylene solubility in toluene at high temperature. Com-
plexes 2 and 3 show higher catalytic activities than 1, probably
the result of the greater stability of their cationic active centers
in toluene. For complex 3, in contract to 1 and 2, the products
are mainly C4 , C6 and C8 and the activity for ethylene oligo-
Chloro(1-naphthyl)[8-(diphenylphosphino)quinoline]nickel(II)
(1). A solution of 8-(diphenylphosphino)quinoline (1.57 g,
5 mmol) in CH2Cl2 (10 mL) was added to a solution of trans-
chloro(1-naphthyl)bis(triphenylphosphane)nickel(II) (3.72 g,
5 mmol) in CH2Cl2 (10 mL), and the reaction mixture was
stirred for 30 min. The resultant solution was concentrated
to about 5 mL and hexane (20 mL) was added to completely
precipitate complex 1. The solid was collected by filtration,
washed with diethyl ether (2 ꢀ 10 mL) and dried under
vacuum to give a deep yellow powder of complex 1 (2.58
g, 97%), mp 233 ꢃC (from CH2Cl2). Found: C, 67.85; H,
4.30; N, 2.25. C31H23ClNNiPꢁ0.75H2O requires C, 67.93;
H, 4.50; N, 2.56%. IR (KBr): n/cmꢂ1 3048.8(s), 2954.7(m),
2864.7(m),1960.3(w),1894.5(w),1827.4(w),760.3(w),1707.5(w),
˚
Table 2 Selected bond lengths (A) and angles (degree) for complex 3
Ni(1)–P(1)
2.2865(10) Ni(1)–Cl(1)
2.4490(10)
2.2653(10)
Ni(1)–N(1)
2.093(3)
2.3439(9)
93.37(9)
Ni(1)–Cl(2)
Ni(1)–Cl(1A)i
N(1)–Ni(1)–Cl(2)
Cl(2)–Ni(1)–P(1)
N(1)–Ni(1)–P(1)
N(1)–Ni(1)–Cl(1)i
P(1)–Ni(1)–Cl(1)i
Cl(1)–Ni(1)–Cl(2)
Cl(1)–Ni(1)–Cl(1)i
84.48(9)
89.37(8)
108.37(4)
92.69(4)
83.76(3)
104.64(4)
Cl(1)i–Ni(1)–Cl(2) 146.99(4)
N(1)–Ni(1)–Cl(1)
P(1)–Ni(1)–Cl(1)
173.11(8)
97.15(4)
Symmetry code i: ꢂx, ꢂy, ꢂz.
1476
New J. Chem., 2002, 26, 1474–1478

View Article Online
Table 3 Oligomerization of ethylene catalyzed by complexes b, 1, 2 and 3a
Proportion (%)
MAO : Nib
T/ꢃC
Activityc
C4
1-C4
C6
1-C6
C8
1-C8
f
f
f
Run No.
Complex
d
1
b
1
1
1
1
1
1
1
1
1
2
2
3
3
3
3
3
3
300 : 1
50 : 1
25
25
25
25
25
25
80
50
0
–
2
0.13
0.42
1.63
0.93
0.91
> 99
92.7
3
100 : 1
300 : 1
500 : 1
1000 : 1
300 : 1
300 : 1
300 : 1
300 : 1
300 : 1
1000 : 1
300 : 1
500 : 1
1000 : 1
500 : 1
500 : 1
500 : 1
88.4
> 99
11.6
22.7
6.9
57.9
65.1
93.7
94.1
4
77.3
93.1
96.3
> 99
> 99
> 99
5
6
3.7
e
–
7
8
0.49
2.05
1.31
2.10
0.91
0.65
1.47
1.53
0.86
2.45
1.75
> 99
83.6
> 99
43
> 99
> 99
> 99
> 99
9
16.4
83.6
10
11
12
13
14
15
16
17
18
ꢂ10
25
25
25
25
25
0
90.7
96.1
77.6
80.2
85.0
86.8
88.4
94.5
9.3
3.9
80.8
94.8
67.1
75.8
88.8
89.2
71.8
64.2
91.0
13.0
15.1
9.4
9.4
4.7
5.6
6.4
5.2
2.0
58.8
64.7
68.4
68.9
57.4
42.0
95.9
95.9
98.0
96.7
94.1
6.8
6.4
50
80
3.5
a
b
Reaction conditions: toluene (50 ml), 4 mmol Ni(II) complex, 1 atm ethylene, 30 min. Molar ratio. c Activity: ꢀ105g C2H4 ( mol Niꢁhꢁatm)ꢂ1
.
d
e
No activity. Very low activity. 1-Cn percentage in its corresponding Cn efin.
f
1588.2(m), 1544.4(m), 1493.6(vs), 1435.8(vs), 1376.0(vs),
1305.7(m),45.2(m),1225.3(m),1198.0(m),1153.3(m),1132.4(m),
1098.5(s), 1069.3(w), 97.2(m), 951.6(m), 852.1(m), 833.0(s),
783.3(vs), 745.6(vs), 695.5(vs), 643.0(w), 69.3(s), 545.3(s),
521.6(w), 495.8(vs), 467.7(s), 419.6(m). 1H NMR(CDCl3): d
6.52 (2H, m), 6.81 (2H, t), 6.89 (2H, t), 7.06 (2H, m), 7.18
(1H, d), 7.39 (1H, d), 7.48 (4H, d), 7.68 (2H, d), 7.83 (1H,
t), 8.06 (1H, d), 8.17–8.23 (2H, m), 8.42 (1H, d, quinolyl-5-
H), 9.11 (1H, d, quinolyl-4-H), 10.20 (1H, d, quinolyl-2-H).
Oligomerization of ethylene
A typical oligomerization reaction was carried out as follows:
to a three-neck flask (250 mL) containing toluene (50 mL)
under ethylene atmosphere (1 atm), was added a dichloro-
methane solution containing either the nickel(II) precatalyst b
(10 mmol) or complex 1, 2 or 3, and an excess amount of
MAO at a given temperature. The solution was stirred for
30 min to allow ethylene oligomerization and the reaction
was terminated by adding acidic ethanol (10% HCl in ethanol).
The products were subsequently analyzed by gas chromato-
graphy or GC-MS analysis.
Chloro(1-naphthyl)[2-methyl-8-(diphenylphosphino) quinoli-
ne]nickel(II) (2). Complex 2 was prepared as a red powder
according to a similar procedure as for complex 1 by using f
instead of 8-(diphenylphosphino)quinoline on the 5 mmol scale
(2.65 g, 97%), mp 178 ꢃC (crystallized from CH2Cl2). Found:
C, 70.18; H, 4.43; N, 2.56. C32H25ClNNiP requires 70.05;
H, 4.59; N, 2.55%. IR (KBr): n/cmꢂ1 3042.9(s), 3004.5(m),
2918.9(w),1966.7(w),1816.7(w),1778.8(w),1667.0(w),1602.6(s),
1544.6(s),1495.4(vs),1436.4(vs),1369.5(s),1308.2(m),1243.5(m),
1220.1(w),1191.0(m),1145.3(m),1101.5(s),1023.3(m),997.3(m),
948.7(m), 893.0(w), 841.9(s), 785.5(vs), 742.2(s), 694.2(vs),
647.6(m), 559.5(s), 541.7(m), 505.9(vs), 481.4(m), 468.2(m),
416.6(m), 393.7(w). 1H NMR(CDCl3): d 3.52 (3H, s, CH3),
6.73–6.85 (5H, m), 7.15 (6H, s), 7.43 (5H, m), 7.74 (1H, s),
7.93 (1H, s), 8.11 (3H, s), 9.76 (1H, s).
X-Ray crystallography
Single crystals of 1 suitable for X-ray analysis were obtained
by recrystallization from CH2Cl2–hexane, while complex 3
was obtained from its CH2Cl2 solution. Intensity data were
collected on a CCD area detector at 293(2) K with graphite
˚
monochromated Mo-Ka radiation (l ¼ 0.71073 A). Cell para-
meters were obtained by global refinement of the positions of
all collected reflections. Intensities were corrected for Lorentz
and polarization effects and empirical absorption. The struc-
tures were solved by direct methods and refined by full-matrix
least-squares on F2. Each H atom was placed in a calculated
position and refined using a riding model. All nonhydrogen
atoms were refined anisotropically. Structure solution and
refinement were performed using the SHELXL-97 package.16
CCDC reference numbers 183920 and 183730. See http://
www.rsc.org/suppdata/nj/b2/b203738f/ for crystallographic
files in cif or other electronic format.
[2-Methyl-8-(diphenylphosphino)quinoline]nickel(II) dichloride
(3). A solution of f (1.64 g, 5 mmol) in CH2Cl2 (10 mL) was
added to a suspension of (Ph3P)2NiCl2 (3.26 g, 5 mmol) in
diethyl ether (20 mL) and the resultant mixture was stirred
for about 30 min. The precipitate was collected by filtration,
washed with diethyl ether and dried under vacuum to give
complex 3 as light green crystals (2.16 g, 95%), mp 240 ꢃC
(from CH2Cl2). Found: C, 50.82; H, 3.61; N, 2.51. C22H18Cl2-
NNiPꢁCH2Cl2 requires C, 50.98; H, 3.72; N, 2.58%; IR (KBr):
n/cmꢂ1 3053.7(s), 1970.6(w), 1911.2(w), 1825.6(w), 1606.6(vs),
1562.6(s), 1502.2(vs),1482.8(s), 1434.5(vs),1368.0(m), 1313.4(s),
1269.9(m), 1246.1(m), 1206.7(w), 1188.1(w), 1146.4(m),
1098.1(s), 1071.6(w), 1028.2(m), 998.3(m), 930.2(w), 893.3(w),
843.9(vs), 779.0(s), 748.0(vs), 695.1(vs), 655.7(m), 618.9(w),
554.1(s), 519.5(s), 504.4(vs), 478.5(s), 461.0(m), 417.5(m).
Crystal data for complex 1. C31H23ClNNiPꢁ0.75H2O,
M ¼ 548.15, red brown block, monoclinic, space group C2/
ꢃ
˚
c, a ¼ 18.606(5), b ¼ 9.184(2), c ¼ 34.005(9) A, a ¼ 90 , b ¼
3
ꢃ
ꢃ
˚
96.381(5) , g ¼ 90 , U ¼ 5774(3) A , Z ¼ 8, m(Mo-Ka) ¼ 0.84
mmꢂ1
,
11609 reflections collected, 5052 unique (Rint
¼
0.0750), R1 ¼ 0.0536 for 2443 reflections with I > 2s(I),
wR2 ¼ 0.1119 for all data.
Crystal data for complex 3. C44H36Cl4N2Ni2P2ꢁ2CH2Cl2 ,
M ¼ 1083.76, light green block, triclinic, space group
˚
P-1, a ¼ 10.9073(7), b ¼ 11.0443(3), c ¼ 11.5761(5) A,
New J. Chem., 2002, 26, 1474–1478
1477

View Article Online
(b) T. R. Younkin, E. F. Connor, J. I. Henderson, S. K. Friedrich,
R. H. Grubbs and D. A. Bansleben, Science, 2000, 287, 460; (c)
F. M. Bauers and S. Merking, Angew. Chem., Int. Ed., 2001,
40, 3020.
(a) P. Braunstein, J. Pietsch, Y. Chauvin, S. Mercier, L. Saussine,
A. DeCian and J. Fischer, J. Chem. Soc., Dalton Trans., 1996,
3571; (b) M. C. Bonnet, F. Dahan, A. Ecke, W. Keim, R. P.
Schulz and I. Tkatchenko, J. Chem. Soc., Chem. Commun.,
1994, 615; (c) P. Braunstein, J. Pietsch, Y. Chauvin, A. DeCian
and J. Fischer, J. Organomet. Chem., 1997, 529, 387; (d ) E. K.
V. D. Beuken, W. J. J. Smeets, A. L. Spek and B. L. Feringa,
Chem. Commun., 1998, 223.
a ¼ 95.605(4)ꢃ, b ¼ 103.724(6)ꢃ, g ¼ 114.101(6)ꢃ, U ¼
3
1206.46(10) A , Z ¼ 2, m(Mo-Ka) ¼ 1.32 mmꢂ1, 8314 reflec-
˚
tions collected, 5387 unique (Rint ¼ 0.0417), R1 ¼ 0.0564 for
4221 reflections with I > 2s(I), wR2 ¼ 0.1497 for all data.
5
Acknowledgements
This work is supported by the Chinese Academy of Sciences
under ‘‘One Hundred Talents’’ and Core Research for Engi-
neering Innovation KGCX203-2, which are greatly acknow-
ledged. WHS thanks Prof. Gerhard Erker of Munster
¨
University and Alexander von Humboldt-Stiftung. We thank
Mr. Steven Schultz for the English proof reading.
6
(a) M. D. Fryzuk, X. Gao and S. J. Rettig, Can. J. Chem., 1995,
73, 1175; (b) J. Pietsch, P. Braunstein and Y. Chauvin, New J.
Chem., 1998, 22, 467.
7
8
N. A. Cooley, S. M. Green, D. F. Wass, K. Heslop, A. G. Orpen
and P. G. Pringle, Organometallics, 2001, 20, 4769.
(a) B. L. Small, M. Brookhart and A. M. A. Bennett, J. Am.
Chem. Soc., 1998, 120, 4049; (b) G. J. P. Britovsek, M. Bruce,
V. C. Gibson, B. S. Kimberley, P. J. Maddox, S. Mastroianni,
S. J. McTavish, C. Redshaw, G. A. Solan, S. Stro¨mberg, A. J. P.
White and D. J. Williams, J. Am. Chem. Soc., 1999, 121, 8728; (c)
G. J. P. Britovsek, V. C. Gibson, B. S. Kimberley, S. Mastroianni,
C. Redshaw, G. A. Solan, A. J. P. White and D. J. Williams,
J. Chem. Soc., Dalton Trans., 2001, 1639.
References
1
2
H. A. Hudali, J. V. Kingston and H. A. Tayim, Inorg. Chem.,
1979, 18, 1391.
(a) W. Keim, F. H. Kowaldt, R. Goddard and C. Krguer, Angew.
¨
Chem., Int. Ed. Engl., 1987, 17, 466; (b) W. Keim, A. Behr,
B. Gruber, B. Hoffmann, F. H. Kowaldt, U. Ku¨rschner, B.
Limba¨cker and F. P. Sistig, Organometallics, 1986, 5, 2356; (c)
W. Keim, Angew. Chem., Int. Ed. Engl., 1990, 29, 235; (d )
W. Keim, J. Mol. Catal., 1989, 52, 19.
9
V. K. Issleib and M. Haftendorn, Z. Anorg. Allg. Chem., 1970,
376, 79.
10 Z. Li, W.-H. Sun, L. Wang, B. Wu, C. He and C. Yan, J. Chem.
Crystallogr., 2002, 32, 107.
11 K. Yamamoto, Bull. Chem. Soc. Jpn., 1954, 27, 501.
12 J. V. Soolingen, H. D. Verkruijsse, M. A. Keegstra and L.
Brandsma, Synth. Commun., 1990, 20, 3153.
13 T. Suzuki, A. Morikawa and K. Kashiwabara, Bull. Chem. Soc.
Jpn., 1996, 69, 2539.
14 E. Bartow and E. W. McCollum, J. Am. Chem. Soc., 1904,
26, 700.
3
(a) L. K. Johnson, C. M. Killian and M. Brookhart, J. Am. Chem.
Soc., 1995, 117, 6414; (b) C. M. Killian, D. J. Tempel, L. K.
Johnson and M. Brookhart, J. Am. Chem. Soc., 1996, 118,
11664; (c) C. M. Killian, L. K. Johnson and M. Brookhart, Orga-
nometallics, 1997, 16, 2005; (d ) S. A. Svejda and M. Brookhart,
Organometallics, 1999, 18, 65; (e) S. P. Meneghetti, P. J. Lutz
and J. Kress, Organometallics, 1999, 18, 2734; ( f ) Z. Li,
W. Sun, Z. Ma, Y. Hu and C. Shao, Chin. Chem. Lett., 2001,
12, 691.
15 K. Sommer, Z. Anorg. Allg. Chem., 1970, 376, 37.
16 G. M. Sheldrick, SHELXTL ver 5.1, Bruker Analytical X-ray
Instruments Inc., Madison, WI, USA, 1998.
4
(a) C. Wang, S. Friedrich, T. R. Younkin, R. T. Li, R. H. Grubbs,
D. A. Bansleben and M. W. Day, Organometallics, 1998, 17, 3149;
1478
New J. Chem., 2002, 26, 1474–1478