N-(2-Benzoylphenyl)benzamido nickel(II) complexes and polymerization reactivity

Article abstract of DOI:10.1016/S0022-328X(03)00235-3

[N-(2-Benzoylphenyl)benzamido-κ²N,O] (η¹-benzyl)(trimethylphosphine)Ni(II) (3) is prepared by the reaction of potassium N-(2-benzoylphenyl)benzamide and Ni(η³-CH₂C₆H₅)Cl (PMe₃).

Full text of DOI:10.1016/S0022-328X(03)00235-3

Journal of Organometallic Chemistry 675 (2003) 72Á76
/
www.elsevier.com/locate/jorganchem
N-(2-Benzoylphenyl)benzamido nickel(II) complexes and
polymerization reactivity
Chang Bo Shim a, Young Heui Kim a, Bun Yeoul Lee a,*, Dong Mok Shin b,
Young Keun Chung b
a Department of Molecular Science and Technology, Ajou University, San 5 Wonchondong, Suwon 442-749, Republic of Korea
b Department of Chemistry and the Center for Molecular Catalysis, College of Natural Sciences, Seoul National University, Seoul 151-742,
Republic of Korea
Received 10 December 2002; received in revised form 31 March 2003; accepted 3 April 2003
Abstract
[N-(2-Benzoylphenyl)benzamido-k2N,O](h1-benzyl)(trimethylphosphine)Ni(II) (3) is prepared by the reaction of potassium N-(2-
benzoylphenyl)benzamide and Ni(h3-CH2C6H5)Cl(PMe3). When 3 is treated with one equivalent of B(C6F5)3, one obtains a
zwitterionic complex, [PhC(O)Ã
/
C6H4Ã
/
NÄ
C(Ph)OB(C6F5)3-k2N,O]Ni(h1-CH2C6H5)(PMe3) (4). When two equivalents of B(C6F5)3
/
is added, PMe3 is abstracted to give a h3-benzyl zwitterionic complex, [PhC(O)Ã
CH2C6H5) (5). Solid structures of 4 and 5 were determined by X-ray crystallography. When ethylene is added to 5, low molecular
/
C6H4Ã
/
NÄ
C(Ph)OB(C6F5)3-k2N,O]Ni(h3-
/
weight polyethylene is obtained.
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Nickel catalyst; Ethylene; Tris(pentafluorophenyl)borane; Zwitterionic complexes
1. Introduction
when ethylene was added to the carboxylato complexes.
The activity and selectivity depend deeply on the nature
of ligand. For example, [(C6H5)2PC6H4C(OB(C6F5)3)O-
k2P,O]Ni(h3-CH2CMeCH2) gives 1-butene with high
efficiency but the complex, [(C6H5)2NC6H4C-
(OB(C6F5)3)O-k2N,O]Ni(h3-CH2CMeCH2), where only
the phosphorus is replaced with nitrogen, is sluggish to
the ethylene and the product is a mixture of 1- and 2-
butene.
Recently, Bazan and I have reported that nickel
complexes containing carboxylato [1,2], carboxamidato
[3], or enamido ligand [4] could be activated by
electrophilic addition reaction of B(C6F5)3 or
Al(C6F5)3. In those cases, B(C6F5)3 or Al(C6F5)3 is
added to the electron-rich oxygen on carbonyl function-
ality or carbon on methylene functionality to afford a
zwitterionic active complex (Eq. 1) [5]. It is significant
that the partially negative boron or aluminium atom is
situated on the side opposite from monomer insertion.
The traditional active species is the presence of a loosely
coordinated base, which competes with the incoming
monomer molecule for the vacant site of lowest energy.
Polyethylene was produced with the carboxamidato and
enamido complexes having bulky substituents on the
ligand frame. However, mainly butene was obtained,
ð1Þ
We were interested in a complex having imine donor,
[(C6H5)2C Ä
NC6H4C(OB(C6F5)3)O-k2N,O]Ni(h3-CH2-
/
C6H5) because imine functionality has been successfully
used for the nickel complexes which is active to the
ethylene polymerisation [6]. The synthesis of the ligand
for the imine complex was reported (Eq. 2) [7].
Nucleophilic attack of phenyllithium to 2-phenyl-1,2-
dihydro-4H-3,1-benzoxazin-4-one, which is commer-
cially available, affords two compounds. One of them
* Corresponding author. Tel.:
2191592.
E-mail address: bunyeoul@ajou.ac.kr (B. Lee).
ꢀ
/
82-31-2191844; fax:
ꢀ/82-31-
0022-328X/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00235-3

C. Shim et al. / Journal of Organometallic Chemistry 675 (2003) 72Á
/76
73
is soluble in diethyl ether, which was assigned to the
imine compound 1 in the literature, and the other is not
soluble in diethyl ether, which was assigned to amide
compound 2. We first tried the metallation with the
ligand assigned to be an imine compound 1 but X-ray
crystallography studies of the resulting complexes re-
vealed that the assignment between two compounds is
not correct. The structure is the one synthesized from
amide compound 2. Herein, we report the synthesis of
the nickel complexes derived from 2 and their reactiv-
ities to ethylene. Metallation to 1 was not successful.
afford a clean complex. Signal of protons on PMe3 at
0.18 ppm as doublet (2JHÃP
10 Hz) and very broad
signal at 1.2Á1.4 ppm for methylene protons on benzyl
ligand are observed in 1H-NMR (C6D6). Single signal is
also observed in 31P{1H}-NMR at ꢂ10.82 ppm. In 19F-
NMR, characteristic signals of pentafluorophenyl group
are observed at ꢂ40.30, ꢂ66.77 and ꢂ72.60 ppm.
ꢁ
/
/
/
/
/
/
ð4Þ
ð2Þ
Single crystals suitable for X-ray crystallography was
obtained by vapor phase addition of pentane to a
benzene solution at room temperature overnight. Fig.
1 shows the structure with selected bond lengths and
angles. It is a NÃ
/
O chelated square planar complex. The
phosphine ligand is situated opposite to the ketone
ligand and the benzyl is to nitrogen atom. The metrical
2. Results and discussion
parameters within the NiÃ
/
NÃ
/
CÃ
/
OÃ
/
B fragment are in
agreement with previously characterized pyridinecar-
2.1. Synthesis and characterization
boxamidoato-Ni(II) and a-iminocarboxamidato-Ni(II)
˚
complexes [3] (distances in A: NiÃ
/
Nꢁ
1.295(7), O(2)Ã
1.518(8)) strongly supporting the zwitterionic structure
depicted in Eq. 4. The distances of NiÃC(1) and NiÃ
/
1.954(5), NÃ
/
Deprotonation of the amide compound 2 is success-
fully carried out with 1.0 equivalent of KH in toluene
for 2 days. Addition of Ni(h3-CH2C6H5)Cl(PMe3) [8] to
the resulting potassium salt affords red crystalline solid
in 77% yield (Eq. 3). Proton signal of PMe3 is observed
C(24)ꢁ
/
1.310(7), C(24)Ã
/
O(2)ꢁ
/
/
Bꢁ
/
/
/P
˚
are 1.977(6) and 2.129(2) A which are comparable with
those observed for neutral carboxamido complex,
{ ( H 3 C ) C [ N C 6 H 5 ] C ( O ) [ N C 6 H 5 ] } N i ( h1 -
at 0.42 ppm as doublet (2JHÃP
signal is observed at 1.8Á1.6 ppm for methylene protons
ꢁ
/
9.6 Hz) and very broad
/
˚
on benzyl ligand in 1H-NMR (C6D6). In 13C{1H}-NMR
spectrum (C6D6), one observes signals at 199.08 and
173.58 ppm which can be assigned to the carbonyl
carbon on ketone and amide. Signals of methylene
carbon on benzyl and methyl carbons on PMe3 are split
CH2C6H5)(PMe3) (1.947(3) and 2.1238(11) A, respec-
tively) [3].
as doublet at 15.62 (2JCÃP
(1JCÃP
29.6 Hz). Although complete assignment of the
ꢁ
/34.2 Hz) and 13.03 ppm
ꢁ
/
carbon signals is not achieved, the number of inequi-
valent carbons and the number of signals are coincided
each other. A single signal is observed in 31P{1H}-NMR
at ꢂ
with the NMR spectra but it is probably amidoÁ
chelated one depicted in Eq. 3 [9].
/
10.55 ppm. The exact structure cannot be argued
/ketone
ð3Þ
Fig. 1. ORTEP view of 4, showing the atom-numbering scheme.
Thermal ellipsoids are shown at 30% probability level. Hydrogen
˚
atoms have been omitted for clarity. Selected bond distances (A) and
angles (8): NiÃ
P, 2.129(2); NÃ
1.518(8); O(1)ÃC(11), 1.237(7); NÃ
84.58(18); O(1)ÃNiÃC(1), 88.1(2); C(1)Ã
97.09(15); C(24)ÃNÃC(19), 119.1(5); C(19)Ã
O(2)ÃB, 131.5(5).
/
N, 1.954(5); NiÃ
C(24), 1.310(7); O(2)Ã
C(19), 1.442(7); NÃ
NiÃP, 90.3(2); NÃ
NÃNi, 112.2(4); C(24)Ã
/
O(1), 1.968(4); NiÃ
C(24), 1.295(7); BÃ
NiÃ
NiÃ
/
C(1), 1.977(6); NiÃ
O(2),
O(1),
P,
/
Addition of one equivalent of B(C6F5)3 to 2 in C6D6
results in clean formation of a complex (Eq. 4) in
contrast with the cases of pyridinecarboxamidato-Ni(II)
and a-iminocarboxamidato-Ni(II) complexes [3], in
which addition of one equivalent of B(C6F5)3 did not
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/

74
C. Shim et al. / Journal of Organometallic Chemistry 675 (2003) 72Á76
/
Addition of two equivalents of B(C6F5)3 affords h3-
benzyl complexes (Eq. 5). PMe3 signals are disappeared
the other face is relatively open. Metrical changes
compared with 4 are a contraction of NÃNi distance
(1.954(5) and 1.905(13) A for 4 and 5, respectively), an
elongation of CÃO distance in ketone (1.237(7) and
1.266(18) A for 4 and 5, respectively) and an elongation
/
1
in H-NMR spectrum and one observes the appearance
˚
of characteristic signals for ortho-protons on h3-benzyl
/
˚
ligand at 5Á6 ppm. In the cases of pyridinecarboxami-
/
˚
O distance (1.518(8) and 1.531(19) A for 4 and 5,
of BÃ
/
doato-Ni(II) and a-iminocarboxamidato-Ni(II) com-
plexes, the two ortho-protons and two methylene
protons on the benzyl ligand are equivalent, respec-
tively, and hence a relatively sharp doublet signal for
ortho-protons and a singlet signal for methylene protons
are observed in 1H-NMR spectra. The equivalency
results from not only the rapid suprafacial shift [10] as
shown below but also equivalency of two faces bisected
by the square plane. In this case, two ortho-protons are
separately observed at 5.81 and 5.59 ppm and the signals
are broad. The two methylene protons are also sepa-
rately observed at 1.07 and 0.34 ppm as broad singlet.
These observations indicate, if the rapid suprafacial shift
is underway still, that the two faces bisected by the
square plane are not equivalent.
respectively). Bite angle (OÃ
/
NiÃN) is enlarged by
/
removing PMe3 ligand (84.58(18) and 87.1(5)8 for 4
and 5, respectively). The other parameters are almost
identical to 4.
2.2. Polymerization studies
Neither 3 nor 4 is active to ethylene. However, rapid
ethylene consumption is observed when ethylene gas is
added to a NMR tube containing 5 in C6D6 but
polyethylene precipitates are not observed. 1H-NMR
spectrum indicates that oligomers are produced. Signals
ð5Þ
Single crystals suitable for X-ray crystallography were
grown from toluene/pentane solution in a freezer and
Fig. 2 shows the results. Structural characterization
reveals a square planar geometry with a trans relation-
ship between the ketone oxygen and the benzyl CH2
carbon. Two faces bisected by the square plane are not
of internal vinyl protons are observed at 5.1Á5.6 ppm
/
but the signals characteristic for the terminal olefins are
not detected. When the ethylene gas is added under the
pressure of 100 psig at room temperature, low molecular
weight polyethylene is obtained. The oligomers are
readily soluble in benzene and the vinyl-end group
signals are observed in 1H-NMR spectrum. Mn is
calculated to be 1200 by using the integration value of
the vinyl and the aliphatic signals in the 1H-NMR
spectrum. 1H-NMR spectrum also indicates that the
polymer is branched one (the branch number, 37/
1000C). The averaged activity for 100 min is 244 kg
molꢂ1 hꢂ1. The complex 5 is also active to the
norbornene polymerization and 850 kg molꢂ1 hꢂ1
activity is observed which is rather lower than that of
[(C6H5)2NC6H4C(OB(C6F5)3)O-k2N,O]Ni(h3-
1
equivalent as expected by its H-NMR spectrum. The
Ph(OB(C6F5)3)CÄ
/
fragment is directed to one face and
CH2CMeCH2) [2].
3. Experimental
3.1. General considerations
Fig. 2. ORTEP view of 5, showing the atom-numbering scheme.
Thermal ellipsoids are shown at 30% probability level. Hydrogen
˚
atoms have been omitted for clarity. Selected bond distances (A) and
All manipulations were performed under an inert
atmosphere using standard glove box and Schlenk
techniques. Toluene, pentane, and C6D6 were distilled
from benzophenone ketyl. Toluene used for polymeriza-
tion reaction was purchased from Aldrich (anhydrous
grade) and purified further over Na/K alloy. Ethylene
was purchased from Conley Gas (99.9%) and purified by
angles (8): NiÃ
NiÃO(1), 1.966(11); NiÃ
1.455(18); O(2)ÃC(21), 1.314(17); O(2)Ã
1.266(18); C(1)ÃC(2), 1.43(2); C(2)ÃC(3), 1.49(3); C(2)Ã
C(3)ÃC(4), 1.39(3); NÃNiÃO(1), 87.1(5); C(20)ÃNÃNi, 115.4(11);
C(21)ÃNÃC(20), 118.1(13); C(21)ÃO(2)ÃB, 137.6(13).
/
C(1), 1.887(17); NiÃ
/
C(2), 2.050(17); NiÃ
C(21), 1.312(18); NÃ
B, 1.531(19); O(1)Ã
/
C(3), 2.20(2);
/
/
N, 1.905(13); NÃ
/
/C(20),
/
/
/C(14),
/
/
/
C(7), 1.38(3);
/
/
/
/
/
/
/
/
/

C. Shim et al. / Journal of Organometallic Chemistry 675 (2003) 72Á
/76
75
3
72.60 (t, JFF
contacting with molecular sieves and copper overnight
under the pressure of 150 psig. Starting material, 2-
3JFF
ꢁ
/
19 Hz), ꢂ
/
ꢁ
/
19 Hz) ppm. 31P{1H}-
NMR (162 MHz, C6D6): d ꢂ10.82 ppm.
/
phenyl-1,2-dihydro-4H-3,1-benzoxazin-4-one
was
phased from Aldrich. NMR spectra were recorded on
a Varian Mercury plus 400. 19F-, 11B-, 31P-NMR spectra
were calibrated and reported downfield from external
3.4. [PhC(O)Ã
/
C6H4Ã
/
NÄ
/
C(Ph)OB(C6F5)3-
k2N,O]Ni(h3-CH2C6H5) (5)
a,a,a-trifluorotoluene, BF3×
/
OEt2 and PPh3, respec-
B(C6F5)3 (0.020 mmol) and 3 (0.010 mmol) were
1
dissolved in C6D6 and H-NMR study was carried out
tively. Elemental analyses were carried out on a Fisons
EA1108 microanalyzer.
with the solution. Three sets of signals are observed in
1H-NMR. The major signals were tentatively assigned
to the desired complex 5 (ca. 60%). One of the minors
was 4 (ca. 20%). Pure complex 5 was synthesized and
isolated according to the following method. Thus, 3
(0.53 mg, 0.10 mmol) and B(C6F5)3 (0.103 mg, 0.200
mmol) were weighed in a vial and toluene (12 ml) was
added. The red solution was stirred for 4 h. The solid
was removed by filtration over celite. The solvent was
removed by vacuum and the residue was dissolved again
in toluene (ca. 1.0 ml). The solid was removed by
filtration over celite again. Pentane (ca. 6 ml) was added
to the filtrate and the solid was removed by filtration
over celite once again. The red crystals suitable for X-
ray crystallography were deposited by storing the filtrate
in a freezer (0.035 g, 36%). 1H-NMR (400 MHz, C6D6):
3.2. [N-(2-Benzoylphenyl)benzamido-k2N,O](h1-
benzyl)(trimethylphosphine)Ni(II) (3)
KH (22.9 mg, 0.571 mmol) and 2 (172 mg, 0.571
mmol) were weighed in a vial and toluene (4 ml) was
added. The mixture was stirred for 2 days, upon which
the hydrogen gas was evolved. Ni(h3-CH2C6H5)-
Cl(PMe3) (149 mg, 0.571 mmol) in toluene (1 ml) was
added. The solution was stirred for 4 h and filtered over
celite. The solvent was removed by vacuum. The residue
was triturated with pentane for 30 min to yield red solid
which is pure by NMR spectra (230 mg, 77%).
Analytically pure crystals were obtained by vapor phase
addition of pentane to a benzene solution. 1H-NMR
(400 MHz, C6D6): d 9.44 (d, Jꢁ
Jꢁ 8.4 Hz, 1H), 7.70 (d, Jꢁ 5.6 Hz, 2H), 7.41 (d, Jꢁ
8.0 Hz, 2H), 7.35 (d, Jꢁ 8.4 Hz, 1H), 7.26Á7.05 (m,
8H), 6.94 (t, Jꢁ 7.6 Hz, 2H), 6.65 (t, Jꢁ
1.8Á CH2), 0.42 (d, Jꢁ
/
7.2 Hz, 2H), 8.54 (d,
d 8.01 (d, Jꢁ
(t, Jꢁ 7.6 Hz, 1H), 7.37 (d, Jꢁ
6.8 Hz, 1H), 6.92Á6.78 (m, 7H), 6.73 (t, Jꢁ
6.62 (br, 1H), 5.81 (br, 1H), 5.59 (br, 1H), 1.07 (br s, 1H,
NiÃCH2), 0.34 (br s, 1H, NiÃ
CH2) ppm. 13C{1H}-NMR
/
7.6 Hz, 1H), 7.69 (d, Jꢁ
7.6 Hz, 2H), 7.24 (t, Jꢁ
7.6 Hz, 1H),
/
7.6 Hz, 2H), 7.42
/
/
/
/
/
/
/
/
/
/
/
/
7.6 Hz, 1H),
9.6 Hz, 9H)
/
1.6 (br, 2 H, NiÃ
/
/
/
/
ppm. 13C{1H}-NMR (100 MHz, C6D6): d 199.08
(carbonyl), 173.58 (carbonyl), 152.32, 149.38, 143.09,
137.22, 134.17, 133.40, 133.14, 131.78, 131.51, 129.87,
(100 MHz, C6D6): d 202.19, 172.04 (carbonyl), 148.1
(dm, 1JFC
137.57, 137.3 (dm, JFC
ꢁ
/
240 Hz), 144.84, 139.8 (dm, 1JFC
ꢁ250 Hz),
/
1
ꢁ250 Hz), 135.27, 135.07,
/
129.77, 128.96, 128.90, 128.79, 128.39, 128.16, 123.44,
2
134.98, 134.38, 133.29, 131.48, 130.47, 130.38, 129.28,
128.71, 128.66, 127.52, 125.07, 121.40 (br, C ÃB), 114.10,
108.81, 103.25 (br), 27.80 ppm. 19F{1H}-NMR (C6D6,
376 MHz): d ꢂ 20 Hz), ꢂ66.57, ꢂ72.55
40.76 (d, 3JFF
20 Hz) ppm. 11B{1H}-NMR (C6D6, 128
MHz): d ꢂ2.2 ppm.
119.93, 15.62 (d, JPC
ꢁ
/
34.2 Hz, NiÃ
/
CH2), 13.03(d,
/
1JPC
C6D6): d ꢂ
68.5; H, 5.76. Found: C, 68.8; H, 6.04%.
ꢁ
/
29.6 Hz, PCH3) ppm. 31P{1H}-NMR (162 MHz,
/10.55 ppm. Anal. Calc. (C30H30NO2PNi): C,
/
ꢁ
/
/
/
3
(t, JFF
ꢁ
/
/
3.3. [PhC(O)Ã
/
C6H4Ã
/
NÄ
/
C(Ph)OB(C6F5)3-
k2N,O]Ni(h1-CH2C6H5)(PMe3) (4)
3.5. Polymerization
Equimolar amount of B(C6F5)3 and 3 (0.010 mmol)
were dissolved in C6D6. The NMR spectra indicated
that a single complex was formed cleanly. Single crystals
suitable for X-ray crystallography and elemental analy-
sis were obtained by vapor phase addition of pentane to
a benzene solution. 13C-NMR spectrum was not
obtained due to its low solubility in benzene and
decomposition in polar solvent as CD2Cl2. 1H-NMR
Complex 3 (10 mmol) and B(C6F5)3 (45 mmol) were
weighed inside a glove box in a 70 ml glass reactor
containing stirring bar. Thirty milliliter of toluene was
added. The reactor was assembled and brought out of
the glove box. The reactor was immersed in a water
bath. The ethylene was fed continuously for 100 min
under the pressure of 100 psig. Ethylene pressure was
released. The volatiles were removed by evacuation to
give waxy solid. Branch numbers were calculated from
the integration value of methyl, methylene, methine
(400 MHz, C6D6): d 8.42 (d, Jꢁ
Jꢁ 6.8 Hz, 2H), 7.52Á7.38 (br, 4H), 7.14Á
7.01 (d, Jꢁ 8.4 Hz, 2H), 7.00 (t, Jꢁ 6.8 Hz, 1H), 6.86
(d, Jꢁ 8.0 Hz, 1H), 6.79 (t, Jꢁ 7.2 Hz, 1H), 6.72 (t, Jꢁ
8.0 Hz, 2H), 6.69 (d, Jꢁ 8.4 Hz, 1H), 1.2Á1.4 (br, 2 H,
NiÃCH2), 0.18 (d, Jꢁ
10 Hz, 9H, PCH3) ppm. 19F{1H}-
NMR (C6D6, 376 MHz): d ꢂ40.3 (br s), ꢂ69.77 (t,
/
7.2 Hz, 2H), 7.46 (d,
/
/
/7.06 (m, 3H),
/
/
1
/
/
/
proton regions in H-NMR spectra.
/
/
Norbornene polymerization was carried out by the
same method and condition reported previously in the
literature [2].
/
/
/
/

76
C. Shim et al. / Journal of Organometallic Chemistry 675 (2003) 72Á76
/
3.6. Crystallographic studies
be obtained free of charge from The Director, CCDC,
12, Union Road, Cambridge CB2 1EZ, UK (Fax: ꢀ44-
1223-336033: e-mail: deposit@ccdc.cam.ac.uk or www:
/
Crystals coated with grease (Apiezon N) were
mounted inside a thin glass tube with epoxy glue and
http://www.ccdc.cam.ac.uk).
placed on an EnrafÁ
/
Nonius CCD single crystal X-ray
Ka
0.71073A). The structures were solved by
diffractometer using graphite-monochromated MoÁ
/
˚
radiation (lꢁ
/
Acknowledgements
direct methods (SHELXS-97) [11] and refined against all
F2 data (SHELXS-97). All non-hydrogen atoms were
refined with anisotropic thermal parameters. The hydro-
gen atoms were treated as idealized contributions.
This work was supported by grant No. (R05-2002-
000-00155-0) from the Basic Research Program of the
Korea Science & Engineering Foundation.
3.6.1. Crystal data for 4
C48H30BF15NNiO2P, Mꢁ
tal size 0.3ꢃ0.3ꢃ0.2 mm, orthorhombic, space group
Pbca, temperature 293(2) K, aꢁ13.0699(2), bꢁ
/
1038.22, red crystals, crys-
References
/
/
/
/
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3
˚
˚
19.8973(3), cꢁ
Dcalcd
1.524 Mg mꢂ3, F(000)ꢁ
collected in h(ꢂ13/13), k(ꢂ20/20), l(ꢂ
in the range 1.178Bu B21.728, Rint 0.0408, 625 para-
meters, 0 restraints, R1ꢁ0.0549, wR2ꢁ0.1633 (for
reflections with I ꢀ2s(I)), R1ꢁ0.0945, wR2ꢁ0.2027,
Goodness-of fitꢁ
hole: 0.589/ꢂ
/
34.8018(6) A, Vꢁ
4192, 9877 reflections
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9050.4(2) A , Zꢁ
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8,
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/
/
(b) B.Y. Lee, X. Bu, G.C. Bazan, Organometallics 20 (2001) 5425.
[4] Y.H. Kim, T.H. Kim, B.Y. Lee, D. Woodmansee, X. Bu, G.C.
Bazan, Organometallics 21 (2002) 3082.
/
1.084, largest difference peak and
ꢂ3
˚
/
0.660 e A
.
[5] Recently other types of zwitterionic active complexes have been
reported, see:(a) C.C. Lu, J.C. Peters, J. Am. Chem. Soc. 124
(2002) 5272.
3.6.2. Crystal data for 5
C45H21BF15NNiO2, Mꢁ
crystal size 0.3ꢃ0.2ꢃ0.15 mm, triclinic, space group
P1; temperature 293(2) K, aꢁ13.083(2), bꢁ13.416(2),
80.321(8), bꢁ
/
962.15, light yellow crystals,
(b) K.S. Cook, W.E. Piers, R. McDonald, J. Am. Chem. Soc. 124
(2002) 5411.
(c) J.W. Strauch, G. Erker, G. Kehr, R. Frohlich, Angew. Chem.
¨
/
/
¯
/
/
˚
cꢁ
71.599(10)8, Vꢁ
Mg mꢂ3, F(000)ꢁ
h(ꢂ12/12), k(ꢂ12/12), l(ꢂ
range 1.608Bu B19.968, Rint
0 restraints, R1ꢁ0.0734, wR2ꢁ
with I ꢀ2s(I)), R1ꢁ0.1871, wR2ꢁ
of-fitꢁ
/
13.397(2) A, aꢁ
/
/
68.169(11), gꢁ
/
Int. Ed. 41 (2002) 2543.
3
˚
/
2067.8(5) A , Zꢁ/2, Dcalcd
ꢁ
/
1.545
[6] (a) T.R. Younkin, E.F. Connor, J.I. Henderson, S.K. Friedrich,
R.H. Grubbs, D.A. Banselben, Science 287 (2000) 460;
(b) L.K. Johnson, C.M. Killian, M. Brookhart, J. Am. Chem.
Soc. 117 (1995) 6414;
/
964, 6664 reflections collected in
12/12), measured in the
0.0951, 586 parameters,
0.1780 (for reflections
0.2812, Goodness-
/
/
/
/
/
ꢁ
/
(c) S.D. Ittel, L.K. Johnson, M. Brookhart, Chem. Rev. 100
(2000) 1169;
/
/
/
/
/
(d) Z. Guan, W.J. Marshall, Organometallics 21 (2002) 3580.
[7] G. Tommasi, P. Bruni, L. Greci, P. Sgarabotto, L. Righi, R.
Petrucci, J. Chem. Soc. Perkin Trans. 2 (1999) 2123.
[8] E. Carmona, M. Paneque, M.L. Poveda, Tetrahedron 8 (1989)
285.
/
0.950, largest difference peak and hole: 0.460/
ꢂ3
˚
ꢂ
/
0.645 e A
.
[9] Recently, a phosphine-ketone chelated Ni(II) complex is reported,
see: W. Liu, J.M. Malinoski, M. Brookhart, Organometallics 21
(2002) 2836.
4. Supplementary material
[10] J.R. Ascenso, M.A.A.F.C.T. Carrondo, A.R. Dias, P.T. Gomes,
M.F.M. Piedade, C.C. Romao, A. Revillon, I. Tkatchenko,
Polyhedron 8 (1989) 2449.
Crystallographic data for structural analysis have
been deposited with the Cambridge Crystallographic
Data Center, CCDC nos. 199002 and 199003 for
compounds 4 and 5). Copies of this information may
[11] G.M. Sheldrick, SHELXL-97, Program for the Refinement of
Crystal Structures, University of Gottingen, Germany, 1997.
¨