Synthesis, characterization and ethylene reactivity of 2- diphenylphosphanylbenzamido nickel complexes

Article abstract of DOI:10.1039/b317033k

Addition of primary amines to N-[2-(diphenylphosphanyl)benzoyloxy] succinimide affords 2-diphenylphosphanylbenzamides, Ph₂PC ₆H₄C(O)NHR (R = C(CH₃)₃, 3; R = H, 4; R = CH₂CH₂CH₃, 5; R = CH(CH ₃)₂, 6). Addition of NiCl(η³-CH ₂C₆H₅)(PMe₃) to the deprotonated potassium salts of the amides and subsequent treatment of two equivalents of B(C₆F₅)₃ to the resulting products furnishes η³-benzyl zwitterionic nickel(II) complexes, [Ph ₂PC₆H₄C(O)NR-κ²N,P] Ni(η³-CH₂C₆H₅) (R = C ₆H₅, 9; R = C(CH₃)₃,10; R = H, 11; R = CH₂CH₂CH₃, 12; R = CH(CH₃) ₂, 13). Solid structures of 9, 11, 13 and the intermediate η¹-benzyl nickel(II) complexes, [Ph₂PC ₆H₄C(O)NR-κ²N,P]Ni(η¹- CH₂C₆H₅)(PMe₃) (R = C ₆H₅, 7; R = C(CH₃)₃, 8) were determined by X-ray crystallography. When ethylene is added to the η³-benzyl zwitterionic nickel(II) complexes, butene is obtained by the complexes 9-12 but complex 13 provides very high molecular-weight branched polyethylene (M_w, ～1300000) with excellent activity (up to 5200 kg mol^-1 h^-1 at 100 psi gauge).

Full text of DOI:10.1039/b317033k

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Synthesis, characterization and ethylene reactivity of
2-diphenylphosphanylbenzamido nickel complexes
Heon Yong Kwon,a Su Yeon Lee,a Bun Yeoul Lee,*a Dong Mok Shinb and Young Keun Chungb
a Department of Molecular Science and Technology, Ajou University, Suwon, 442-749 Korea.
E-mail: bunyeoul@ajou.ac.kr; Fax: 82-31-219-1592; Tel: 82-31-219-1844
b School of Chemistry and Center for Molecular Catalysis, Seoul National University,
Seoul 151-747, Korea
Received 6th January 2004, Accepted 11th February 2004
First published as an Advance Article on the web 24th February 2004
Addition of primary amines to N-[2-(diphenylphosphanyl)benzoyloxy]succinimide affords 2-diphenylphosphanyl-
benzamides, Ph2PC6H4C(O)NHR (R = C(CH3)3, 3; R = H, 4; R = CH2CH2CH3, 5; R = CH(CH3)2, 6). Addition
of NiCl(η3-CH2C6H5)(PMe3) to the deprotonated potassium salts of the amides and subsequent treatment of
two equivalents of B(C6F5)3 to the resulting products furnishes η3-benzyl zwitterionic nickel() complexes,
[Ph2PC6H4C(O)NR-κ2N,P]Ni(η3-CH2C6H5) (R = C6H5, 9; R = C(CH3)3, 10; R = H, 11; R = CH2CH2CH3,
12; R = CH(CH3)2, 13). Solid structures of 9, 11, 13 and the intermediate η1-benzyl nickel() complexes,
[Ph2PC6H4C(O)NR-κ2N,P]Ni(η1-CH2C6H5)(PMe3) (R = C6H5, 7; R = C(CH3)3, 8) were determined by X-ray
crystallography. When ethylene is added to the η3-benzyl zwitterionic nickel() complexes, butene is obtained by
the complexes 9–12 but complex 13 provides very high molecular-weight branched polyethylene (Mw, ∼1300000)
with excellent activity (up to 5200 kg molϪ1 hϪ1 at 100 psi gauge).
Introduction
Results and discussion
Since Brookhart and co-workers1 and Gibson and co-workers2
reported that late transition metal complexes could serve as
catalysts for polymerization of olefins, there have been con-
siderable activity to develop commercially viable catalyst
in both academic and industrial fields.3,4 Lee, Bazan and co-
workers have reported carboxylato,5,6 carboxamido,7,8 enamido
nickel complexes9 that can be activated by electrophilic addi-
tion of Lewis-acidic B(C6F5)3 or Al(C6F5)3 to the electron-rich
oxygen or carbon atom. By the activation reaction, zwitterionic
complexes are provided in which the anion is located on a site
removed from the monomer insertion trajectory. The novel
activation reaction was successfully expanded to the zirconium
and hafnium complexes.10 Recently catalysts based on various
types of zwitterionic organometallic complexes have drawn
much attention.11
Synthesis and characterization
Ph2PC6H4C(O)NHPh (2) is prepared by the reported method:
i.e., 1,3-dicyclohexylcarbodiimide-mediated coupling reaction
of Ph2
PC H CO H (1) with aniline.12 The other amide com-
6
4
2
pounds, 3–6 are not obtained by the similar conditions but can
be prepared in 85–91% yields by addition of the correspond-
ing amines to N-[2-(diphenylphosphanyl)benzoyloxy]succin-
imide, which is prepared easily from 1 [eqn. (1)].13 Attempts
to prepare analogous compound with sterically more bulky
2,6-dimethylaniline and 2,6-diisopropylaniline using various
conditions were not successful.
In case of the late transition metal complexes, balance
between the chain propargation and the chain transfer rates is
regulated mainly by steric factor. High molecular-weight poly-
ethylene is obtained by sterically congested complexes such as
(1)
[(H C)C{᎐N(2,6-(Me CH) C H )}C{OB(C F ) }{᎐N(2,6-(Me -
᎐
᎐
3
2
2
6
3
6
5
3
2
CH) C H )}]Ni(η3-CH C H )7 and[(H C)C{᎐N(2,6-(Me CH) -
᎐
2
6
3
2
6
5
3
2
2
C H )}C{CH X(C F ) }{᎐N(2,6-(Me CH) C H )}]Ni(η3-CH -
᎐
6
3
2
6
5
3
2
2
6
3
2
C6H5) (X = B or Al), where the axial sites of the square plane
are blocked by the isopropyl group.9 Recently, we reported an
example showing that electronic effect of the ligand also plays
an important role in determining the molecular weight of the
products. While the 2-diphenylphosphanylbenzoato and 2-di-
phenylaminobenzoato nickel() complexes gave mainly butene
by the rapid chain transfer reaction, the 2-alkylideneamino-
benzoato nickel() complexes (imine functionality) provided
polyethylene.6 Any big steric differences on the axial sites were
not detected between the two solid structures. We report herein
preparation and ethylene reactivity of zwitterionic diphenyl-
phosphanylbenzamido nickel() complexes, [Ph2PC6H4C{OB-
(C6F5)3}NR-κ2N,P]Ni(η3-CH2C6H5) (R = C6H5, C(CH3)3, H,
CH2CH2CH3, CH(CH3)2). In these complexes, it is also
observed that slight change in the ligand frame results in big
difference on the products. Phenylamido complex (R = C6H5)
gives 1-butene but isopropylamido complex (R = CH(CH3)2)
provides very high molecular-weight polyethylene with excel-
lent activity.
Deprotonation of 2 with 1.0 equivalent KH in THF affords
the potassium salt. Addition of NiCl(η3-CH2C6H5)(PMe3) to
the potassium salt furnishes the desired η1-benzyl trimethyl-
phosphine complex 7. A very broad benzyl-CH2 signal is
observed at 1.5–1.8 ppm in the 1H NMR spectrum (C6D6) sug-
gesting that the complex is under some fluxional motion. Two
31P-signals are observed at Ϫ15.8 and Ϫ40.2 ppm as doublets
with huge coupling constant (2JPP = 341 Hz), which suggests
that the two phosphorus atoms are in a trans-relationship.
Reaction of the potassium salt of 3 with NiCl(η3-CH2C6H5)-
(PMe3) provides the η1-benzyl complexes 8 either. In this
case, a sharp benzyl-CH2 signal is observed at 1.69 ppm as a
doublet of doublets by coupling with the two phosphorus
1
atoms (3JPH = 14.8, 8.4 Hz) in the H NMR spectrum (C6D6).
Relatively sharp 31P-singnals are observed at Ϫ21.9 and Ϫ46.8
ppm as doublets with huge coupling constant (2JPP = 401 Hz).
Single crystals of 7 and 8, which are suitable for X-ray crystallo-
T h i s j o u r n a l i s © T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 4
D a l t o n T r a n s . , 2 0 0 4 , 9 2 1 – 9 2 8
921

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Table 1 Selected bond distances (Å) and angles(Њ)
Entry
7
8
9
11a
13
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
Ni–N
1.981(7)
1.355(10)
1.224(9)
1.972(3)
1.334(6)
1.245(5)
1.9311(18)
1.303(3)
1.307(2)
1.522(3)
1.953(3)
2.109(3)
2.330(3)
2.1039(11)
1.897(4), 1.908(5)
1.286(7), 1.283(7)
1.309(6), 1.303(6)
1.519(6), 1.522(7)
1.967(6), 1.953(7)
2.032(7), 2.025(7)
2.210(7), 2.211(6)
2.1187(16), 2.1230(16)
1.948(5)
1.297(7)
1.299(6)
1.520(7)
1.944(7)
2.109(8)
2.417(11)
2.0975(18)
NiN–CO
NiNC–O
NiNCO–B
Ni–CH2
1.981(8)
1.989(4)
Ni–Cipso
Ni–Cortho
Ni–PPh2
Ni–PMe3
N–Ni–PPh2
Ph2P–Ni–CH2
Ni–N–CO
Ni–C–Cipso
N–C–O
2.185(3)
2.179(3)
84.9(2)
2.1812(13)
2.1913(14)
83.82(12)
98.93(15)
126.0(3)
102.1(3)
127.0(4)
95.62(6)
92.65(10)
131.90(16)
75.27(17)
119.24(19)
135.59(17)
133.0
88.7
Ϫ146.1
Ϫ149.8
91.75(13), 92.33(14)
100.4(2), 98.1(2)
133.7(3), 134.2(4)
71.5(4), 77.6(4)
125.6(4), 126.3(5)
128.6(4), 129.5(5)
2.2, 7.5
92.10(17)
96.3(3)
125.4(4)
76.0(5)
117.8(5)
140.3(4)
Ϫ155.8
Ϫ66.0
167.4
129.5
97.9(3)
131.1(6)
108.9(6)
125.5(9)
C–O–B
N–C–O–B
N–Ni–PPh –C
Ϫ55.9
172.7
135.4
44.9
Ϫ175.3
Ϫ126.4
Ϫ164.6, 69.4
Ϫ160.0, 74.8
ipso on Ph
2
bPPh –Ni–N–C
2
18
a Two independent molecules are present in the asymmetric unit cell. b Carbon not connected to oxygen atom.
graphy, are obtained by layer-diffusion of pentane to toluene
solutions. The signals in the 1H NMR spectra of the complexes
obtained by the reaction of the potassium salts of 4–6 with
NiCl(η3-CH2C6H5)(PMe3) are too broad to be analyzed and the
resulting η1-benzyl complexes cannot be isolated by crystal-
lization.
Solid structures of 7 and 8 are shown in Fig. 1 and 2, respect-
ively, and the selected bond distances and angles are tabulated
in Table 1. The complexes show distorted square planar struc-
tures with a trans relationship between the two phosphine
ligands, which is in agreement with the observation of huge
phosphorus–phosphorus coupling constants in the 31P NMR
spectra. Distortion is more severe in the more bulky t-butyl
complex 8 and interplane angles between N–Ni–PPh2 and
C–Ni–PMe3 planes are 27.25(23) and 44.20(9)Њ for 7 and 8,
respectively. The C–O distances (1.224(9) and 1.245(5) Å for 7
and 8, respectively) are consistent with a double bond between
these two atoms. The Ni–N, Ni–CH2 and Ni–PMe3 distances
(entries 1, 5 and 9) are slightly longer than those observed
for α-iminocarboxamide complex [(H C)C(᎐NPh)C(O)NPh]-
᎐
3
Ni(η1-CH2C6H5)(PMe3) (1.936(2), 1.947(3) and 2.1238(11) Å,
respectively).7
Addition of two equivalents of B(C6F5)3 to the η1-benzyl
trimethylphosphine complex 7 results in clean formation of a
zwitterionic η3-benzyl complex 9 (Scheme 1). Sharp benzyl-CH2
signal is observed at 0.74 ppm as doublet by the coupling with
the phosphorus atom (3JHP = 4.8 Hz) in the 1H NMR spectrum
(C6D6). Observation of the up-field shifted signals of benzyl-
aromatic protons (6.08, 6.48 and 6.54 ppm for ortho-, meta- and
para-protons, respectively) indicates formation of the zwit-
terionic η3-benzyl complexes.7 A sharp single signal is observed
at Ϫ33.05 ppm as a singlet in the 31P NMR spectrum. Addition
of two equivalents of B(C6F5)3 to 8 does not afford a single
complex. Two signals are observed at Ϫ30.78 and Ϫ35.20 ppm
as singlets in the 31P NMR spectrum (C6D6). Two benzyl-CH2
signals are observed as doublets at 1.02 (3JHP = 2.8 Hz) and 1.49
ppm (3JHP = 2.8 Hz) with 5 : 1 ratio and two C(CH3)3 signals are
observed at 0.96 and 0.71 ppm with the same ratio as well.
Attempt to separate the isomers by recrystallization was not
successful. It can be postulated that the sets of isomers arise
from the pseudorotamers of the benzyl ligand. Similar isomer-
Fig. 1 Thermal ellipsoid plot (30% probability level) of 7.
Scheme 1 (i) KH; (ii) NiCl(η3-CH2C6H5)(PMe3); (iii) B(C6F5)3 (2.0
eq).
Fig. 2 Thermal ellipsoid plot (30% probability level) of 8.
D a l t o n T r a n s . , 2 0 0 4 , 9 2 1 – 9 2 8
922

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ism was observed for the pyridinecarboxamido and α-imino-
carboxamido η3-benzyl nickel complexes.7,8,14
Reaction of the potassium salts of 4–6 with NiCl(η3-CH2-
C6H5)(PMe3) and subsequent addition of two equivalents of
B(C6F5)3 to the resulting complexes furnish the desired
η3-benzyl complexes, 11–13 (Scheme 1). The complexes were
isolated by recrystallization and were characterized by NMR
spectroscopy and the elemental analysis. Isomerism observed
for 10 is not observed for these complexes and only one set of
signals is observed. The benzyl-CH2 signals are observed as
doublets at 0.85–1.06 ppm in the 1H NMR spectra (C6D6) and
the signals of the benzyl aromatic protons are observed in the
up-field shifted region, 6.0–7.0 ppm. A single 31P signal is
observed at Ϫ29 to Ϫ32 ppm and 11B and 19F NMR spectra are
in agreement with the zwitterionic η3-benzyl complexes.
Single crystals of 9, 11 and 13, which are suitable for X-ray
crystallography, were obtained by layer-diffusion of pentane to
benzene solutions and the solid structures were determined.
Fig. 3, 4 and 5 show the structures and the selected bond
distances and angles are tabulated in Table 1. All three com-
plexes show η3-benzyl square planar structures with a trans
relationship between the nitrogen and the methylene carbon.
Elongations of C–O distances and contractions of NiN–CO
distances compared with those observed for 7 and 8 are indi-
cative of the zwitterionic structures (entries 2 and 3). The Ni–N,
Ni–PPh2 and Ni–CH2 distances observed for the zwitterionic
complexes 9, 11 and 13 are, respectively, shorter than the corre-
sponding distances observed for the neutral η1-benzyl com-
plexes, 7 and 8 (entries 1, 8 and 5). The development of positive
charge on the nickel atom might result in stronger Ni–N,
Ni–PPh2 and Ni–CH2 bonds. The Ni–C–Cipso angles observed
for the complexes 9, 11 and 13 are substantially reduced in their
η3-character when compared with those observed for the
η1-benzyl complexes 7 and 8 (entry 13). The angles of N–Ni–
PPh2 observed for 9, 11 and 13 are bigger than those observed
for 7 and 8 (entry 10). Complex 13 has the longest Ni–N
distance and the shortest Ni–CH2 distance among the three
Fig. 5 Thermal ellipsoid plot (30% probability level) of 13.
η3-benzyl complexes (entries 1 and 5). The variation among
Ni–CH2, Ni–Cipso and Ni–Cortho distances observed for 13 is
relatively big while that observed for 11 is small (entries 5, 6
and 7).
The steric hindrance on the axial sites is of importance in
controlling the molecular weight of polyethylene. By blocking
the axial sites, high molecular-weight polyethylene is usually
obtained. The boron atom is located on a plane formed by
N–C–O atoms in complex 11 (dihedral angle of N–C–O–B,
2.2Њ) and consequently B(C6F5)3 does not impose any steric
hindrance on the axial sites. In complexes 9 and 13, the boron
atoms are not located on the N–C–O plane (dihedral angles
of N–C–O–B, 133.0 and Ϫ155.8Њ for 9 and 13, respectively)
but the B(C6F5)3 is located so far away from the nickel centre
that it exerts a minimal amount of steric hindrance on the axial
sites. One of the phenyls attached on the phosphorus atom is
directed almost perpendicular to the square plane in complex 9
ipso on
(the dihedral angle of N–Ni–PPh –C
Ph, 88.7Њ) and con-
2
sequently exerts some steric hindrance on an axial site. Some
steric blocking on an axial site by the phenyl group can be also
expected for 11 and 13 even though the dihedral angles of
ipso on Ph
N–Ni–PPh –C
are not as perpendicular as that observed
2
for 9 (dihedral angles, 69.4 and Ϫ66.0Њ for 11 and 13, respect-
ively). The other phenyls are located laterally to the square
plane and consequently impose minimal amount of steric hin-
drance on the axial sites. Steric blocking by the group attached
on the nitrogen atom is not expected for 11 because the attached
hydrogen is too small. The isopropyl and phenyl groups
attached to the nitrogen atom in 9 and 13 are directed biased to
ipso on Ph
the square plane (the dihedral angles of PPh –Ni–N–C
2
and PPh –Ni–N–CHisopropyl, Ϫ149.8 and 129.5Њ, respectively)
2
and consequently only slight steric blocking on the axial site is
expected but the methyl groups on the isopropyl unit are
slightly bent toward nickel, which might result in slightly more
steric hindrance on the axial site. One of the axial sites appears
to be widely open in both of the structures of 9 and 13, but
some shielding of the site by the π-electrons on the benzamide
ring can be expected for 13 because the angle between the
square plane and the benzamide benzene ring is fairly steep
(Fig. 6). The angle observed for 9 is not so steep as that
observed for 13. Interplane angles between N–Ni–PPh2 plane
and the benzamido benzene plane are calculated to be
38.18(0.10) and 63.93(0.14)Њ for 9 and 13, respectively. The dif-
ference around nickel centres between 9 and 13 is shown in
Fig. 6.
Fig. 3 Thermal ellipsoid plot (30% probability level) of 9.
Ethylene reactivity studies
When ethylene gas was added to a toluene solution of 9
(10 µmol) under the pressure of 100 psi gauge at room temper-
ature, the temperature of the solution rises to 41 ЊC in 2 min by
heat of reaction but neither the precipitation of polymers nor
the increase of viscosity of the solution is observed. Analysis of
Fig. 4 Thermal ellipsoid plot (30% probability level) of 11.
D a l t o n T r a n s . , 2 0 0 4 , 9 2 1 – 9 2 8
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Table 2 Ethylene reactivitya
Entry
Complex
T b /ЊC
Time/min
P/psi gauge
Ac
930e
Mw/103
Mw/Mn
T m/ЊC
Branchesd
1
2
3
9
10
11
12
13
13
13
13
13
13
25
25
25
25
25
25
50
50
50
80
10
10
10
10
3.2
4.8
1.5
2.3
5.0
10
100
100
100
100
100
75
100
75
50
1-Butene
1-Butene
1-Butene ϩ 2-butene
1-Butene
3.0
2.8
3.9
3.7
3.7
e
e
240
230
4
300e
2300
1400
5200
1900
1600
0
5f
6f
7f
8f
9f
10
1300
1700
1070
1350
1300
120
121
113
112
108
20
20
60
60
60
100
a Polymerization conditions: 30 mL toluene, 10 µmol of complex ϩ 25 µmol of B(C6F5)3 as a scavenger. b Initial bath temperature. c Activity in kg
1
mol-NiϪ1
h
Ϫ1). d Determined by H NMR and corresponds to the number of branches/1000 carbons. e Averaged activity measured by flow meter.
f 5 µmol of complex and 13 µmol of B(C6F5)3 as a scavenger were used and stirring was ceased at the stated time.
between the square plane and the benzamide benzene ring.
The angle is fairly steep in the polymerization catalyst 13
[38.18(0.10)Њ] while relatively wide angle is observed for the
dimerization catalyst 9 [63.93(0.14)Њ]. In case that the angle is
steep as observed for 13, shielding of the other axial site by
π-electrons on the benzamide ring might be expected.
Conclusion
Zwitterionic 2-diphenylphosphanylbenzamido nickel() com-
plexes [Ph2PC6H4C(O)NR-κ2N,P]Ni(η3-CH2C6H5) (R = C6H5,
9; R = C(CH3)3, 10; R = H, 11; R = CH2CH2CH3, 12; R =
CH(CH3)2, 13) were prepared. Solid structures of 9, 11, 13 and
the intermediate η1-benzyl nickel() complexes, [Ph2PC6H4-
C(O)NR-κ2N,P]Ni(η1-CH2C6H5)(PMe3) (R = C6H5, 7; R =
C(CH3)3, 8) were determined by X-ray crystallography. Com-
plex 9 is highly active with ethylene, giving 1-butene. Complexes
10, 11 and 12 show rather low activities, giving mainly butene
too. Complex 13 provides very high molecular-weight poly-
ethylene (Mw, ∼1300000) with excellent activity (up to 5200 kg
molϪ1 hϪ1 activity at 100 psi gauge).
Fig. 6 Comparison around Ni centres between 9 and 13.
the solution by the 1H NMR spectroscopy indicates that
1-butene is formed. The measurement of the total consumed
ethylene gas by flow meter for 10 min gives the activity of 930
kg molϪ1 hϪ1 (Table 2, entry 1). Additions of ethylene gas to the
complexes 10–12 by the same method give mainly butene with
relatively low activities (230–300 kg molϪ1
h
Ϫ1, entry 2–4).
However, addition of ethylene gas to 13 under the same condi-
tion gives precipitates of polymer. The activity is so high that
the temperature rises to 60 ЊC in 3.2 min and stirring is ceased.
The activity is calculated to be 2300 kg molϪ1 hϪ1 by measure-
ment of the weight of the obtained polymer (entry 5). When the
polymerization temperature is raised to 50 ЊC, the activity
increases to 5200 kg molϪ1 hϪ1 (entry 7), which is the highest
value among the activities observed for the similar-type zwit-
terionic nickel complexes.5–9 Observation of activity decrease by
decrease of the pressure is consistent with other nickel catalysts
(entry 7–9). The complex is so unstable at 80 ЊC that no poly-
mer is obtained at the temperature (entry 10). The molecular
weight of the polymers is considerably high (Mw, ∼1300000).
Similar high molecular-weight polyethylenes were obtained
with enamido nickel complexes having bulky substituents,
Experimental
General remarks
All manipulations were performed under an inert atmosphere
using standard glove box and Schlenk techniques. Toluene,
pentane, THF and C6D6 were distilled from benzophenone
ketyl. Methylene chloride was dried by distillation over
CaH2. Toluene used for polymerization 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 contacting with molecular sieves and
copper for 3 days under the pressure of 150 psi gauge. NMR
spectra were recorded on a Varian Mercury plus 400. 19F
NMR (376 MHz), 11B NMR (128 MHz) and 31P NMR
(162 MHz) spectra were calibrated and reported downfield
from external α,α,α-trifluorotoluene, BF3ؒOEt2 and PPh3,
respectively. Elemental analyses were carried out at the Inter-
University Center Natural Science Facilities, Seoul National
University. Gel permeation chromatograms (GPC) were
obtained at 140 ЊC in trichlorobenzene using Waters Model
150-Cϩ GPC and the data were analyzed using a polystyrene
analyzing curve. Differential scanning calorimetry (DSC) was
performed on a Thermal Analysis 3100. Diphenylphosphanyl-
N-phenylbenzamide (2),12 N-(2-diphenylphosphanylbenz-
oyloxy)succinimide,13 and Ni(η3-CH2C6H5)Cl(PMe3)6 were
prepared according to the literature methods.
[(H C)C{᎐N(2,6-(Me CH) C H )}C{CH X(C F ) }{᎐N(2,6-
᎐
᎐
3
2
2
6
3
2
6
5 3
(Me2CH)2C6H3)}]Ni(η3-CH2C6H5) (X = B or Al).9 Rather
broad molecular weight distributions (MWD, 2.8–3.7) were
observed presumably due to the failure to keep the polymeriz-
ation conditions homogeneous by the formation of a very
viscous polymerization solution. Analysis of the polymer by
1H NMR spectroscopy and DSC indicate that the polymers
have a branched structure and branch number increases by
the increase of polymerization temperature.
It is not easy to explain why complex 9 gives 1-butene while
complex 13 providing very high molecular-weight polyethylene.
When the two solid structures of 9 and 13 are compared
(Fig. 6), an axial site of each complex seems to be shielded by
almost same amount by a phenyl group attached on the phos-
phorus atom and the phenyl or the isopropyl group attached on
the nitrogen atom. A big difference is observed on the angles
N-(t-Butyl)-2-diphenylphosphanylbenzamide (3)
Synthesis of the compound by using expensive 1-(3-dimethyl-
aminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI) in
D a l t o n T r a n s . , 2 0 0 4 , 9 2 1 – 9 2 8
924

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relatively low yield (36%) was previously described.15 See
below for more convenient and inexpensive synthesis. To a flask
containing N-(2-diphenylphosphanylbenzoyloxy)succinimide
(1.00 g, 2.48 mmol) in methylene chloride (10 mL) was added
t-butylamine (0.52 mL, 5.0 mmol). The solution was stirred for
3 h. Water (10 mL) was added and the organic phase was col-
lected. The compound was extracted further from the water
phase with additional methylene chloride (10 mL × 3). The
organic phases were combined and dried over anhydrous
MgSO4. Removal of solvent gave a residue, which was crystal-
lized from methylene chloride and hexane (v/v, 20 : 1) at Ϫ20 ЊC
overnight (0.82 g, 91%).
1 H, Ph–H6) ppm. 13C{1H} NMR (CDCl3): δ = 22.80 (CH3),
2
42.35 (CH(CH3)2), 128.45 (d, JPC = 6.8 Hz, C3), 128.81 (d,
3JPC = 6.9 Hz, PPh-meta), 128.93, 129.04 (PPh-para), 130.11,
134.07 (d, 2JPC = 20.4 Hz, PPh-ortho), 134.07, 137.01 (d, 1JPC
=
11.3 Hz, PPh-ipso), 168.19 (carbonyl) ppm. 31P{1H} NMR
(CDCl3): δ = Ϫ9.52 ppm. Anal. Calc. for C22H22NOP: C, 76.06;
H, 6.38; N, 4.03. Found: C, 75.94; H, 6.43; N, 4.04%.
[Ph2PC6H4C(O)NPh-ꢀ2P,N ]Ni(ꢁ1-CH2C6H5)(PMe3) (7)
To a flask containing compound 2 (400 mg, 1.05 mmol) in THF
(1.0 mL) was added KH (42.1 mg, 1.05 mmol) and the solution
was stirred overnight. The solution was filtered and solvent was
removed by vacuum to give a residue, which was triturated in
pentane to give white solid in nearly quantitative yield. The 1H
NMR spectrum of the potassium salt in C6D6 is too broad to be
analyzed. To a flask containing the potassium salt (150 mg,
0.358 mmol) dissolved in toluene (1.0 mL) was added a solution
of NiCl(η3-CH2C6H5)(PMe3) (93 mg, 0.36 mmol) in toluene
(0.5 mL). The solution was stirred for 1 h. It was filtered over
celite and solvent was removed under vacuum. Single crystals,
which were analytically pure and suitable X-ray crystallo-
graphy, were obtained by layer-diffusion of pentane to a tolu-
ene solution at room temperature. One benzene molecule was
2-Diphenylphosphanylbenzamide (4)
The compound was synthesized according to the same condi-
tions and procedure for 3 using N-(2-diphenylphosphanylbenz-
oyloxy)succinimide (1.00 g, 2.48 mmol) and NH3. NH3 gas was
added using a balloon at room temperature. The compound
was purified by column chromatography on silica gel eluting
with methylene chloride and ethyl acetate (v/v, 10 : 1). Yield =
0.67 g (89%). Mp 150 ЊC. IR (KBr): 1645 (carbonyl), 3192, 3372
1
(NH2) cmϪ1. H NMR (CDCl3): δ = 5.84 (br s, 1 H, NH), 6.05
(br s, 1 H, NH), 6.97 (ddd, 3JHH = 7.6 Hz, 3JHP = 4.0 Hz, 4JHH
=
1.6 Hz, 1 H, Ph–H3), 7.20–7.38 (m, 12 H, Ph–H4 and 5 and PPh2),
7.64 (ddd, 3JHH = 7.6 Hz, 4JHP = 3.6 Hz, 4JHH = 1.6 Hz, 1 H, Ph–
H6) ppm. 13C{1H} NMR (CDCl3): δ = 127.90 (d, 2JP, C = 4.6 Hz,
incorporated in the crystal lattice. Yield = 156 mg (64%). H
1
NMR (C6D6): δ = 0.66 (d, 2JHP = 8.8 Hz, 9 H, PCH3), 1.68 (br s,
3
2 H, benzyl-CH2), 6.87–7.28 (m, 21 H), 8.70 (ddd, JHH
=
3
3
4
C3), 127.94 (d, JP, C = 6.9 Hz, PPh-meta), 128.56, 128.69 (PPh-
7.6 Hz, JHP = 4.0 Hz, JHH = 1.2 Hz, 1 H, Ph–H6), 8.84 (d,
3JHH = 8.0 Hz, 2 H, benzyl-Ho) ppm. 13C{1H} NMR (C6D6):
δ = 11.50 (d, 1JCP = 22.8 Hz, PCH3), 19.64 (benzyl-CH2), 119.71,
122.19, 123.64, 123.69, 125.83, 126.51, 126.61, 126.78, 127.27,
127.74, 128.30, 128.59, 129.98, 130.06, 144.07, 144.20, 145.05,
147.29, 165.37 (carbonyl) ppm. 31P{1H} NMR (C6D6):
δ = Ϫ40.2 (d, JPP = 341 Hz), Ϫ15.8 (d, JPP = 341 Hz) ppm.
Anal. Calc. for C35H35NNiOP2ؒC6H6: C, 71.94; H, 6.05; N, 2.05.
Found: C, 71.82; H, 6.00; N, 2.12.
2
para), 130.43, 133.71 (d, JP, C = 20.5 Hz, PPh-ortho), 134.11,
1
1
135.53 (d, JPC = 19.7 Hz, C2), 136.81 (d, JPC = 19.9 Hz, PPh-
ipso), 139.70 (d, JPC = 24.3 Hz, C1), 170.43 (carbonyl) ppm.
2
31P{1H} NMR (CDCl3): δ = Ϫ8.35 ppm. Anal. Calc. for
C19H16NOP: C, 74.74; H, 5.28; N, 4.59. Found: C, 74.80; H,
5.38; N, 4.58%.
2
2
2-Diphenylphosphanyl-N-propylbenzamide (5)
The compound was synthesized according to the same condi-
tions and procedure for 3 using N-(2-diphenylphosphanylbenz-
oyloxy)succinimide (0.800 g, 1.98 mmol) and n-propylamine
(0.33 mL, 4.0 mmol). The compound was purified by column
chromatography on silica gel eluting with methylene chloride.
Yield = 0.600 g (87%). Mp 102 ЊC. IR (KBr): 1630 (carbonyl),
3296 (NH) cmϪ1. 1H NMR (CDCl3): δ = 0.83 (t, 3JHH = 7.2 Hz,
3 H, CH3), 1.35 (sextet, 3JHH = 7.2 Hz, 2 H, NCH2CH2), 3.21 (q,
3JHH = 7.2 Hz, 2 H, NCH2), 5.94 (br s, 1 H, NH), 6.92 (ddd, 3JHH
= 7.2 Hz, 3JHP = 4.0 Hz, 4JHH = 1.2 Hz, 1 H, Ph–H3), 7.20–7.38
[Ph2PC6H4C(O)NC(CH3)3-ꢀ2P,N ]Ni(ꢁ1-CH2C6H5)(PMe3) (8)
The compound was synthesized according to the same condi-
tions and procedure for 7 using 3 (0.23 g, 0.57 mmol). Single
crystals, which were analytically pure and suitable X-ray crys-
tallography, were obtained by layer-diffusion of pentane to a
toluene solution at room temperature. One molecule of benzene
was incorporated in the crystal lattice. Isolated yield = 0.26 g
(69%). 1H NMR (C6D6): δ = 0.88 (d, 2JHP = 7.2 Hz, 9 H, PCH3),
3
1.58 (s, 9 H, CH3) 1.69 (dd, JPH = 14.8, 8.4 Hz, 2 H, benzyl-
3
4
(m, 12 H, Ph–H4and 5 and PPh2), 7.57 (ddd, 3JHH = 7.2 Hz, 4JHP
=
CH2), 6.80–7.40 (m, 18 H), 8.64 (ddd, JHH = 7.2 Hz, JHP =
4
3.6 Hz, JHH = 1.2 Hz, 1 H, Ph–H6) ppm. 13C{1H} NMR
3.6 Hz, 4JHH = 1.2 Hz, 1 H, Ph–H6) ppm. 13C{1H} NMR (C6D6):
δ = 14.62 (d, 1JCP = 20.4 Hz, PCH3), 22.95 (benzyl-CH2), 29.89
(C(CH3)3), 53.82 (C(CH3)3), 124.15, 128.58, 128.87, 129.72,
129.75, 129.96, 130.18, 130.37, 130.39, 131.41, 131.49, 133.32,
133.44, 134.82, 134.90, 147.07, 147.10, 147.12, 148.42, 148.57,
167.36 (carbonyl) ppm. 31P{1H} NMR (C6D6): δ = Ϫ46.8 (d,
(CDCl3): δ = 11.56 (CH3), 22.55 (CH2), 41.72 (NCH2), 127.79
2
3
(d, JPC = 4.6 Hz, C3), 128.44 (d, JPC = 6.9 Hz, PPh-meta),
2
128.59, 128.69 (PPh-para), 129.83, 133.68 (d, JPC = 19.7 Hz,
PPh-ortho), 133.80, 135.35 (d, JPC = 19.7 Hz, C2), 136.70 (d,
1
1JPC = 10.6 Hz, PPh-ipso), 141.58 (d, 2JPC = 25.8 Hz, C1), 168.69
(carbonyl) ppm. 31P{1H} NMR (CDCl3): δ = Ϫ9.28 ppm. Anal.
Calc. for C22H22NOP: C, 76.06; H, 6.38; N, 4.03. Found: C,
75.93; H, 6.45; N, 4.04%.
2JPP = 401 Hz), Ϫ21.9 (d, JPP = 401 Hz) ppm. Anal. Calc. for
2
C33H39NNiOP2ؒC6H6: C, 70.50; H, 6.84; N, 2.11. Found: C,
70.65; H, 6.71; N, 2.21.
N-Isopropyl-2-diphenylphosphanyl benzamide (6)
[Ph2PC6H4C{OB(C6F5)3}NPh-ꢀ2P,N ]Ni(ꢁ3-CH2C6H5) (9)
The compound was synthesized according to the same condi-
tions and procedure for 3 using N-(2-diphenylphosphanyl-
benzoyloxy)succinimide (0.600 g, 1.49 mmol) and isopropyl-
amine (0.25 mL, 3.0 mmol). The crude residue was crystallized
from methylene chloride at Ϫ20 ЊC overnight. Yield = 0.44 g
Compound 7 (30 mg, 0.040 mmol) and B(C6F5)3 (45 mg, 0.110
mmol) were weighed in a vial and toluene (0.5 mL) was added
at room temperature. The solution was stirred for 1 h. The white
precipitates of B(C6F5)3ؒPMe3 were filtered off. The solution
was layered with pentane in a 5 mm NMR tube. Red crystals,
which were analytically pure and suitable for X-ray crystallo-
graphy, were obtained after overnight at room temperature.
(85%). Mp 177 ЊC. IR (KBr): 1626 (carbonyl), 3280 (NH) cmϪ1
.
1H NMR (CDCl3): δ = 1.02 (d, 3JHH = 6.8 Hz, 6 H, CH3), 4.08
3
3
1
3
(septet, JHH = 6.8 Hz, 1 H, CH(CH3)2), 5.68 (br d, JHH
=
Yield = 35 mg (76%). H NMR (C6D6): δ = 0.74 (d, JHP
=
3
3
6.8 Hz, 1 H, NH), 6.89 (ddd, JHH = 7.6 Hz, JH,P = 4.0 Hz,
4.8 Hz, 2 H, benzyl-CH2), 6.08 (d, 3JHH = 7.6 Hz, 2 H, benzyl-
4JHH = 1.6 Hz, 1 H, Ph–H3), 7.20–7.38 (m, 12 H, Ph–H4 and 5 and
Ho), 6.44 (d, JHH = 7.6 Hz, 2 H, NPh–Ho), 6.48 (t, JHH
=
3
3
3
4
4
PPh2), 7.57 (ddd, JHH = 7.6 Hz, JHP = 3.6 Hz, JHH = 1.6 Hz,
7.6 Hz, 2 H, benzyl-Hm), 6.54 (t, 3JHH = 7.6 Hz, 1 H, benzyl-Hp),
D a l t o n T r a n s . , 2 0 0 4 , 9 2 1 – 9 2 8
925

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3
4
or
6.59 (td, JHH = 7.2 Hz, JHH = 2.0 Hz, 1 H, Ph–H4 5), 6.66
(ddd, 3JHP = 10.4 Hz, 3JHH = 8.0 Hz, 4JHH = 1.2 Hz, 1 H, Ph–H3),
6.81 (t, 3JHH = 7.6 Hz, 1 H, NPh–Hp), 6.90–7.37 (m, 13 H), 8.30
0.75C6H6: C, 56.84; H, 2.61; N, 1.37. Found: C, 56.46; H, 2.42;
N, 1.25%.
(dd, JHH = 7.2 Hz, JHP = 3.4 Hz, 1 H, Ph–H6) ppm. 13C{1H}
NMR (C6D6): δ = 29.50 (d, 2JCP = 7.6 Hz, benzyl-CH2), 114.23,
119.41, 121.27 (br, ipso-CB), 124.83, 124.87, 127.07, 127.47,
129.33, 129.43, 130.03, 130.56, 131.77, 132.00, 132.04, 133.09,
3
4
[Ph2PC6H4C{OB(C6F5)3}N(CH2)2CH3-ꢀ2P,N ]Ni(ꢁ3-CH2C6H5)
(12)
The compound was synthesized according to the same condi-
tions and procedure for 11 using the potassium salt of 5. The
intermediate η1-benzyl complex could not be isolated. Red
crystals, which were analytically pure, were obtained by layer-
diffusion of pentane to a toluene solution at room temperature.
Overall yield = 40%. 1H NMR (C6D6): δ = 0.43 (t, 3JHH = 7.2 Hz,
1
133.20, 134.10, 134.23, 137.00 (dm, JCF = 259 Hz) 137.36,
137.50, 139.56 (dm, 1JCF = 253 Hz), 144.88, 148.19 (dm, 1JCF
=
244 Hz), 164.51 (d, JCP = 3.8 Hz, carbonyl) ppm. 19F{1H}
3
NMR (C6D6): δ = Ϫ101.25 (t, JFF = 18.4 Hz, Fm), Ϫ96.47 (t,
3
3JFF = 19.9 Hz, Fp), Ϫ69.41 (br s, Fo) ppm. 31P{1H} NMR
(C6D6): δ = Ϫ33.05 ppm. 11B{1H} NMR (C6D6): δ = Ϫ1.77 ppm.
Anal. Calc. for C50H26BF15NNiOP: C, 57.67; H, 2.52; N, 1.35.
Found: C, 57.62; H, 2.61; N, 1.35%.
3
3 H, CH3), 0.68–0.80 (m, 2 H, CH2), 0.85 (d, JHP = 4.0 Hz,
2 H, benzyl-CH2), 2.25 (t, 3JHH = 8.0 Hz, 2 H, NCH2), 6.21 (d,
3JHH = 7.2 Hz, 2 H, benzyl-Ho), 6.46 (td, J = 8.0, 1.2 Hz, 1 H,
or
3
Ph–H4 5), 6.50 (t, JHH = 7.6 Hz, 1 H, benzyl-Hp), 6.85 (t,
3JHH = 7.6 Hz, 2 H, benzyl-Hm), 6.90–7.14 (m, 12 H), 8.19 (dd,
3JHH = 7.6 Hz, 4JHP = 4.4 Hz, 1 H, Ph–H6) ppm. 13C{1H} NMR
[Ph2PC6H4C{OB(C6F5)3}NC(CH3)3-ꢀ2P,N ]Ni(ꢁ3-CH2C6H5)
(10)
2
(C6D6): δ = 11.65 (CH3), 24.41 (CH2), 28.41 (d, JCP = 6.4 Hz,
The compound was synthesized according the same conditions
and method for 9 using 8 (0.096 g, 0.145 mmol). Red solid was
obtained by layer-diffusion of pentane to a toluene solution at
room temperature. Two sets of signals are observed in 5 : 1
ratio. The signals for the minor isomer are marked in italic
benzyl-CH2), 50.06 (NC), 116.44, 118.15, 118.21, 121.90 (br,
ipso-CB), 125.60, 126.01, 128.52, 128.79, 129.18, 129.29,
129.42, 130.08, 130.25, 130.32, 130.56, 131.61, 131.84, 133.08,
1
133.18, 133.29, 133.64, 133.76, 133.98, 137.28 (dm, JCF
=
1
259 Hz), 138.57, 138.71, 139.84 (dm, JCF = 253 Hz), 148.47
1
1
3
characters. Yield = 0.064 g (43%). H NMR (C6D6): δ = 0.71
(dm, JCF = 244 Hz), 162.56 (d, JCP = 5.0 Hz, carbonyl) ppm.
and 0.96 (s, 9 H, CH3), 1.02 and 1.49 (d, 3JHP = 2.8 and 4.4 Hz,
19F{1H} NMR (C6D6): δ = Ϫ101.11 (t, JFF = 18.1 Hz, Fm),
3
3
2 H, benzyl-CH2), 6.42 (d, JHH = 7.6 Hz, 2 H, benzyl-Ho),
Ϫ95.59 (t, JFF = 19.6 Hz, Fp), Ϫ69.88 (d, JFF = 19.6 Hz, Fo)
ppm. 31P{1H} NMR (C6D6): δ = Ϫ29.59 ppm. 11B{1H} NMR
(C6D6): δ = Ϫ3.02 ppm. Anal. Calc. for C47H29BF15NNiOP: C,
55.98; H, 2.91; N, 1.39. Found: C, 56.08; H, 2.84; N, 1.35%.
3
3
or
5
6.48–6.56 (m, 2 H, Ph–H4
and benzyl-Hp), 6.80–7.28 (m,
14 H), 8.10 (dd, JHH = 7.2 Hz, JHP = 4.4 Hz, 1 H, Ph–H6)
ppm. 13C{1H} NMR (C6D6): δ = 26.83 (d, 2JCP = 8.4 Hz, benzyl-
CH2), 27.50 and 29.04 (C(CH3)3), 53.98 and 57.91(N–C),
118.01, 121.58, 122.02 (br, ipso-CB), 124.92, 125.35, 128.73,
129.06, 129.17, 129.25, 129.36, 130.18, 130.28, 130.34, 131.50,
131.97, 132.40, 132.64, 133.57, 133.68, 133.91, 134.04, 134.74,
3
4
[Ph2PC6H4C{OB(C6F5)3}NCH(CH3)2-ꢀ2P,N ]Ni(ꢁ3-CH2C6H5)
(13)
137.29 (dm, 1JCF = 253 Hz), 139.01, 139.14, 139.82 (dm, 1JCF
=
The compound was synthesized according to the same condi-
tions and method for 11 using the potassium salt of 6. The
intermediate η1-benzyl complex could not be isolated. Red
single crystals, which were analytically pure and suitable for
X-ray crystallography, were obtained by layer-diffusion of pen-
tane to a toluene solution at room temperature. Overall yield =
1
253 Hz), 148.47 (dm, JCF = 243 Hz), 160.93 (carbonyl) ppm.
31P{1H} NMR (C6D6): δ = Ϫ35.20 and Ϫ30.78 ppm. 11B{1H}
NMR (C6D6): δ = Ϫ2.14 ppm. Anal. Calc. for C48H30BF15-
NNiOP: C, 56.40; H, 2.96; N, 1.37. Found: C, 56.32; H, 2.96; N,
1.34%.
1
3
40%. H NMR (C6D6): δ = 0.62 (d, JHH = 6.8 Hz, 6 H, CH3),
3
3
[Ph2PC6H4C{OB(C6F5)3}NH-ꢀ2P,N ]Ni(ꢁ3-CH2C6H5) (11)
0.81 (d, JHP = 4.4 Hz, 2 H, benzyl-CH2), 3.73 (septet, JHH
=
6.8 Hz, 1 H, CH(CH3)2), 6.43 (d, 3JHH = 8.0 Hz, 2 H, benzyl-Ho),
6.49 (td, J = 8.0, 1.2 Hz, 1 H, Ph–H4 or 5), 6.51 (t, 3JHH = 7.6 Hz,
1 H, benzyl-Hp), 6.97 (t, 3JHH = 7.6 Hz, 2 H, benzyl-Hm), 6.90–
The potassium salt of 4 (100 mg, 0.291 mmol) and NiCl-
(η3-CH2C6H5)(PMe3) (76 mg, 0.29 mmol) were weighed in a vial
and toluene (4.0 mL) was added. The solution was stirred for
2 h at room temperature. The solution was filtered over celite
and the solvent was removed under vacuum. The residue was
dissolved in toluene (4.0 mL) and B(C6F5)3 (298 mg, 0.582
mmol) was added. The solution was stirred for 2 h and the
precipitates of B(C6F5)3ؒPMe3 were filtered off. The solution
was layered with pentane to give orange single crystals, which
were analytically pure and suitable for X-ray crystallography.
One and half molecules of benzene and two crystallo-
graphically independent molecules are present in the asym-
metric unit cell. Overall yield = 125 mg (42%). 1H NMR (C6D6):
δ = 1.06 (d, 3JHP = 3.6 Hz, 2 H, benzyl-CH2), 4.57 (s, 1 H, NH),
6.03 (d, 3JHH = 7.2 Hz, 2 H, benzyl-Ho), 6.65 (t, 3JHH = 7.6 Hz,
1 H, benzyl-Hp), 6.70 (t, 3JHH = 7.6 Hz, 1 H, Ph–H4 or 5), 6.88–
7.04 (m, 12 H), 7.09 (t, 3JHH = 7.6 Hz, 2 H, benzyl-Hm), 8.69 (dd,
3JHH = 7.6 Hz, 4JHP = 4.4 Hz, 1 H, Ph–H6) ppm. 13C{1H} NMR
(C6D6): δ = 30.87 (d, 2JCP = 6.8 Hz, benzyl-CH2), 114.82, 115.59,
115.67, 119.86 (br, ipso-CB), 126.70, 127.08, 128.53, 129.05,
129.11, 129.21, 129.56, 130.87, 130.94, 131.56, 131.59, 132.19,
132.16, 132.54, 132.80, 132.92, 133.01, 133.10, 133.60, 137.33
(dm, 1JCF = 257 Hz), 137.97, 138.09, 139.93 (dm, 1JCF = 263 Hz),
148.30 (dm, 1JCF = 240 Hz), 167.45 (d, 3JCP = 5.3 Hz, carbonyl)
ppm. 19F{1H} NMR (C6D6): δ = Ϫ100.76 (t, 3JFF = 18.1 Hz, Fm),
3
4
7.14 (m, 12 H), 8.24 (dd, JHH = 7.6 Hz, JHP = 4.4 Hz, 1 H,
Ph–H6) ppm. 13C{1H} NMR (C6D6): δ = 22.72 (C(CH3)2), 27.52
2
(d, JCP = 6.4 Hz, benzyl-CH2), 50.82 (NC), 117.82, 120.56,
121.90 (br, ipso-CB), 125.26, 125.69, 128.80, 129.08, 129.18,
129.82, 130.18, 130.26, 130.56, 131.60, 133.00, 133.32, 133.43,
1
133.56, 134.27, 137.20 (dm, JCF = 233 Hz), 138.37, 138.50,
1
1
139.74 (dm, JCF = 248 Hz), 148.39 (dm, JCF = 238.9 Hz),
162.36 (carbonyl) ppm. 19F{1H} NMR (C6D6): δ = Ϫ101.15 (t,
3JFF = 18.4 Hz, Fm), Ϫ95.54 (t, 3JFF = 19.9 Hz, Fp), Ϫ69.73 (br s,
Fo) ppm. 31P{1H} NMR (CDCl3): δ = Ϫ28.78 ppm. 11B{1H}
NMR (C6D6): δ = 0.0 ppm. Anal. Calc. for C47H28BF15NNiOP:
C, 55.99; H, 2.81; N, 1.39. Found: C, 55.66; H, 2.92; N 1.38%.
General ethylene polymerization
Toluene (30 mL) and B(C6F5)3 were added in a 60 mL glass
reactor containing stirring bar inside glove box. The reactor
was assembled and brought out from the glove box. The reactor
was immersed in an oil bath of which temperature had been set
to a given value. The solution was stirred for 15 min, at which
time the temperature of the solution reached the bath temper-
ature. A solution of complex 9–13 in toluene (1.0 mL) was
injected with syringe to the reactor. The ethylene was fed con-
tinuously for a given time under the pressure. The reaction was
quenched by release of ethylene pressure. In case of the form-
ation of soluble oligomers, several drops of the solution were
3
3
Ϫ94.98 (t, JFF = 19.9 Hz, Fp), Ϫ70.10 (d, JFF = 19.9 Hz, Fo)
ppm. 31P{1H} NMR (C6D6): δ = Ϫ32.12 ppm. 11B{1H} NMR
(C6D6): δ = Ϫ3.46 ppm. Anal. Calc. for C44H22BF15NNiOPؒ
D a l t o n T r a n s . , 2 0 0 4 , 9 2 1 – 9 2 8
926

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Table 3 Crystal data and structure refinement for 7, 8, 9, 11 and 13a
7
8
9
11
13
Formula
Mw
a/Å
b/Å
c/Å
α/Њ
β/Њ
C35H35NNiOP2ؒC6H6 C33H39NNiOP2ؒC6H6 C50H26BF15NNiOP [C44H22BF15NNiOP]2ؒ1.5C6H6 C47H28BF15NNiOP
684.40
664.41
24.6360(10)
13.7920(10)
21.9550(10)
90
108.448(2)
90
7076.5(7)
Monoclinic
C2/c
1042.21
37.7580(10)
12.0400(10)
20.9810(10)
90
109.45(6)
90
8993.8(9)
Monoclinic
C2/c
2049.39
1008.19
12.5838(4)
15.4674(5)
22.3179(8)
90
89.4179(16)
90
4343.7(3)
Monoclinic
P21/n
12.0570(10)
12.1230(10)
13.9160(10)
102.270(5)
109.119(5)
95.366(4)
1848.4(3)
Triclinic
14.9305(4)
17.2883(6)
20.1574(6)
92.828(2)
105.688(2)
106.531(2)
4757.0(3)
Triclinic
γ/Њ
V/Å3
Crystal system
Space group
Dc/g cmϪ1
Z
¯
P1
¯
P1
1.230
2
0.643
1.247
8
0.669
13742
8101
401
0.0715
0.1598
1.538
8
0.569
18092
10292
631
0.0456
0.0996
1.431
2
1.542
4
0.587
22317
8540
607
0.0957
0.2362
µ/mmϪ1
0.537
32685
21169
1235
0.1042
0.3106
No. of data collected 8431
No. of unique data
No. of variables
R
5613
406
0.0914
0.1593
Rw
a Data collected at 293(2) K with Mo Kα radiation (λ(Kα) = 0.7107 Å), R(F) = Σ||Fo| Ϫ |Fc||/Σ|Fo| with Fo > 2.0σ(I ), Rw = [Σ[w(Fo2 Ϫ Fc2)2]/Σ[w(Fo)2]2]1/2
with Fo >2.0σ(I ).
4 For recent progress, see: E. F. Connor, T. R. Younkin, J. I.
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dissolved in C6D6 and the analysis of the oligomers was carried
out by NMR spectroscopy. In the case of formation of poly-
mers, the reaction mixture was poured into a flask containing
100 mL acetone. The white participates were collected by fil-
tration and dried under vacuum. Branch numbers were calcu-
lated from the integration value of methyl, methylene, methine
proton regions in the 1H NMR spectra. 1H NMR spectra of the
polymers were obtained at 100 ЊC in benzene-d6 and 1,2,4-
trichlorobenzene (v/v, 4 : 1).
Crystallographic studies
A single crystal coated with grease (Apiezon N) were mounted
inside a thin glass tube with epoxy glue and placed on an Enraf-
Nonius CCD single crystal X-ray diffractometer. The structures
were solved by direct methods (SHELXS-97)16 and refined
against all F 2 data (SHELXS-97). All non-hydrogen atoms
were refined with anisotropic thermal parameters. The hydro-
gen atoms were treated as idealized contributions. The crystal
data and refinement results are summarized in Table 3 and the
selected bond distances and angles are tabulated in Table 1.
CCDC reference numbers 228028–228032.
See http://www.rsc.org/suppdata/dt/b3/b317033k/ for crystal-
lographic data in CIF or other electronic format.
5 Z. J. A. Komon, X. Bu and G. C. Bazan, J. Am. Chem. Soc., 2000,
122, 1830; Z. J. A. Komon, X. Bu and G. C. Bazan, J. Am. Chem.
Soc., 2000, 122, 12379; B. Y. Lee, Y. H. Kim, H. J. Shin and C. H.
Lee, Organometallics, 2002, 21, 3481; Z. J. A. Komon, G. M.
Diamond, M. K. Leclerc, V. Murphy, M. Okazaki and G. C. Bazan,
J. Am. Chem. Soc., 2002, 124, 15280.
6 C. B. Shim, Y. H. Kim, B. Y. Lee, Y. Dong and H. Yun,
Organometallics, 2003, 22, 4272.
7 B. Y. Lee, G. C. Bazan, J. Vela, Z. J. A. Komon and X. Bu, J. Am.
Chem. Soc., 2001, 123, 5352.
Acknowledgements
This work was supported by the Ministry of Science and Tech-
nology of Korea through Research Center for Nanocatalysis,
one of the National Science Programs for Key Nano-
technology.
8 B. Y. Lee, X. Bu and G. C. Bazan, Organometallics, 2001, 20, 5425;
C. B. Shim, Y. H. Kim, B. Y. Lee, D. M. Shin and Y. K. Chung,
J. Organomet. Chem., 2003, 675, 72.
9 Y. H. Kim, T. H. Kim, B. Y. Lee, D. Woodmansee, X. Bu and
G. C. Bazan, Organometallics, 2002, 21, 3082.
10 Y. H. Kim, T. H. Kim, N. Y. Kim, E. S. Cho, B. Y. Lee, D. M. Shin
and Y. K. Chung, Organometallics, 2003, 22, 1503; Y. Zhang,
D. A. Kissounko, J. C. Fettinger and L. R. Sita, Organometallics,
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11 G. Erker, Chem. Commun., 2003, 1469; T. J. Woodman,
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D a l t o n T r a n s . , 2 0 0 4 , 9 2 1 – 9 2 8
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D a l t o n T r a n s . , 2 0 0 4 , 9 2 1 – 9 2 8
928