Ethylene/polar norbornene copolymerizations by bimetallic salicylaldimine-nickel catalysts

Article abstract of DOI:10.1021/ma051344i

Bimetallic salicylaldimine-nickel complexes, bridge{[(2,6-iPr ₂C₆H₂)-N=CH-(2-anthracenyl-C₆H ₃-O)-κ₂-N,O]Ni(η³-CH ₂)}₂ (bridge = ortho-C₆H_4<

Full text of DOI:10.1021/ma051344i

Macromolecules 2005, 38, 10027-10033
10027
Ethylene/Polar Norbornene Copolymerizations by Bimetallic
Salicylaldimine-Nickel Catalysts
Sujith S,† Dae June Joe,† Sung Jae Na,† Young-Whan Park,‡ Cheol Ho Choi,§ and
Bun Yeoul Lee*,†
Department of Molecular Science and Technology, Ajou University, Suwon 443-749 Korea; LG Chem
Ltd./Research Park, 104-1, Munji-dong, Yuseong-gu, Daejon 305-380, Korea; and Department of
Chemistry, College of Natural Sciences, Kyungpook National University, Taegu 702-701, Korea
Received June 23, 2005; Revised Manuscript Received September 16, 2005
ABSTRACT: Bimetallic salicylaldimine-nickel complexes, bridge{[(2,6-iPr2C6H2)-NdCH-(2-anthracenyl-
C6H3-O)-κ2-N,O]Ni(η3-CH2Ph)}2 (bridge ) ortho-C6H4, 10; bridge ) CH2, 11; bridge ) ortho-C6H4(C6H4)2,
12), are prepared. The bimetallic complexes 10-12 show higher activities and higher polar monomer
incorporations in the ethylene/2-(methoxycarbonyl)norbornene and ethylene/2-(acetoxymethyl)norbornene
copolymerizations than the mononuclear complex, [(2,6-iPr2C6H3)-NdCH-(2-anthracenyl-C6H3-O)-κ2-N,O]-
Ni(η3-CH2Ph) (13).
Introduction
bound species to the olefin-bound isomer, from which
the chain growth occurs, can be efficiently triggered by
using a bimetallic system, consequently leading to
increase of either activity or the polar monomer incor-
poration (eq 1). Marks also reported bimetallic systems
could incorporate significantly higher amount of styrene
in the ethylene/styrene copolymerizations by cooperative
action between the two metal centers.10
The conventional Ziegler-Natta catalysts containing
group 4 transition metals are not applicable for polym-
erization of polar monomers because of high oxophilicity
of the early transition metals. Incorporation of polar
monomers into nonpolar polyethylene backbone has
been achieved only after protection of the polar func-
tional groups.1 Since late transition metals are less
oxophilic than the early transition metals, the catalysts
containing the late transition metals are more func-
tional group tolerant and thus applicable to the polym-
erization of polar monomers.2,3 Especially, neutral nickel
complexes that do not require such an activator as
methylaluminoxane (MAO) are attractive for the po-
lymerization of polar monomers. Since Grubbs reported
salicylaldimine-based neutral nickel complexes could
serve as catalysts for ethylene/(functionalized nor-
bornene) copolymerizations and ethylene homopolymer-
izations in the presence of polar impurities such as
ether, ketone, esters, alcohol, or amine,4,5 various neu-
tral nickel catalysts have been prepared,6 and some of
them have been successfully applied for polymerization
of the polar monomers.7 Recently, ethylene polymeriza-
tions even in water phase have been achieved with the
neutral nickel catalysts producing polyethylene latex.8
However, addition of polar monomers or the presence
of polar impurities leads to significant decrease of the
activity, and the incorporations of the polar monomers
are limited in some copolymerizations. Either the low
activity or the low incorporation of the polar monomer
is possibly attributed to the coordination of the polar
group to the active metal center. Ziegler predicted that
the O-bound species should be more favorable over the
olefin-bound isomer in the case of vinyl acetate addition
to the nickel catalyst and Grubbs proved it experimen-
tally.9 We envisioned that the shift from the polar group-
Results and Discussion
Synthesis and Characterization. We recently re-
ported the synthesis of diamino compound 1, from which
macrocyclic and acyclic dinuclear zinc complexes were
successfully prepared for cyclohexene oxide/CO2 copo-
lymerizations.11 The methylene-bridged compound 2 is
prepared by the literature method,12 and compound 3
is prepared by the similar method applied for the
synthesis of 1 (eq 2). Schiff’s base condensation between
3-anthracenylsalicylaldehyde and diamino compounds
1-3 affords bis(salicylaldimine) compounds 4-6 (Scheme
1). The bulky anthracenyl and isopropyl groups are
attached in the ligand framework since it was reported
that they are essential to acquire high activity and high
molecular weight.4,5 The characteristic feature of these
ligand systems is that the N-N separations do not
change by the conformational variations triggered by
any allowed rotational movement around C-C bonds.
That is, the bridging unit is rigid. The nickel-nickel
separations in the prepared complexes can be modulated
a little by the variation of the dihedral angle between
the two chelating planes. The variation of the dihedral
† Ajou University.
‡ LG Chem Ltd./Research Park.
§ Kyungpook National University.
* Corresponding author. E-mail: bunyeoul@ajou.ac.kr.
10.1021/ma051344i CCC: $30.25 © 2005 American Chemical Society
Published on Web 11/05/2005

10028 S et al.
Macromolecules, Vol. 38, No. 24, 2005
Scheme 1a
a Legend: (i) 3-anthracenylsalicylaldehyde, Dean-Stark; (ii) KH and then (η3-CH2C6H5)NiCl(PMe3); (iii) B(C6F5)3.
angle is triggered by the allowed rotation around the
the phosphine-free fast initiating system, (salicylaldi-
mine)Ni(Me)(NCCH3), by reacting the neutral ligand
with (tmeda)NiMe2.5 The advantage of the η3-benzyl-
(salicylaldimine)Ni complexes over the (salicylaldimine)-
Ni(Me)(NCCH3) is that only a single isomer is formed
for the η3-benzyl complexes. For the (salicylaldimine)-
Ni(Me)(NCCH3), two isomers were observed by the cis-
trans isomerism. The presence of the cis-trans isom-
erism gives rise to three isomers in the case of the
dinuclear complexes and a rather complex set of the 1H
NMR signals are observed when an equimolar amount
of (tmeda)NiMe2 is added to 4-6.
C-C bond(s) or C-N bond.11b
Polymerization Studies. When the ethylene gas is
added to complexes 10-12 in toluene under 100 psig
pressure, temperature rises rapidly by exothermic reac-
tion and viscous solution was obtained (Table 1). For
complexes 10 and 12, the temperature can be controlled
in the range of 45-60 °C with an ice bath, and the
obtained polymers show narrow molecular weight dis-
tributions (Mw/Mn, 3.0 and 3.5), indicating presence of
a single active species (entries 1 and 4). However, the
temperature cannot be controlled even with the ice bath
and reaches up to 84 and 89 °C for methylene-bridged
complex 11 and mononuclear complex 13, respectively
(entries 2 and 5). The polymers obtained from the
uncontrolled batches show very broad molecular weight
distributions (Mw/Mn, 16 and 15). Polymers of narrow
molecular weight distributions are obtained by cutting
the polymerization time to 5 min, at which time the
temperature does not exceed 62 °C (entries 3 and 6).
The activities of the dinuclear complexes (1900-3000
kg/(mol of Ni h)) are comparable to that of the mono-
nuclear complex 13 (2400 kg/(mol of Ni h)). The DSC
study of the polymers obtained by 10, 12, and 13
exhibits a sharp melting centered at 122, 117, and 120
°C, respectively, indicating the presence of some branches
in the polyethylene backbone. Interestingly, the polymer
obtained with CH2-bridged dinuclear complex 11 exhib-
its two endothermic transitions: a broad one centered
at ∼94 °C and a sharp one centered at 114 °C (entry 3).
The η1-benzyl-PMe3-nickel(II) complexes 7-9 are
prepared in 73-80% yields by reacting the potassium
salt of 4-6 with (η3-CH2C6H5)NiCl(PMe3) (Scheme 1).13
The 1H, 13C, and 31P NMR spectra are in agreement with
the structures. The benzyl-CH2 signal is observed at
0.84-0.90 ppm as a doublet by the coupling with
phosphorus (3JPH ) 6.0-7.2 Hz) in the 1H NMR spectra.
The NdCH proton signal is also observed at 8.01-8.04
ppm as doublet by the coupling with phosphorus (4JPH
) 8.4 Hz). The number of signals in the 13C NMR
spectra is in agreement with the number of inequivalent
carbons in the structure. Single signal is observed at
5.06-5.35 ppm in the 31P NMR spectra.
B(C6F5)3 has been effectively used for PMe3-abstract-
ing reagent to generate phosphine-free η3-benzyl com-
plexes which show fast initiation for olefin polymeriza-
tions.14 Addition of equivalent amount of B(C6F5)3 to the
η1-benzyl-PMe3-nickel(II) complexes 7-9 affords a
single clean complex. The 1H and 13C NMR spectra
strongly support the formation of the PM3-free η3-benzyl
1
1
Branch numbers calculated by the analysis of the H
complexes 10-12 (Scheme 1). In the H NMR spectra,
NMR spectra of the polymers are in agreement with the
DSC data. The higher the branches, the lower the
melting temperature. The higher incorporation of
branches observed for complexes 11 and 12 might be
attributed to a cooperative action between the two metal
centers. Marks has also reported that dinuclear CGC-
type catalysts could generate some branches by feeding
only ethylene gas by cooperative action of the two metal
centers.15 Molecular weights of the polymers obtained
the PMe3-methyl signal disappears completely, and the
characteristic η3-benzyl signals are observed upfield
shifted at 6.03, (triplet, meta), 6.18 (doublet, ortho), and
1
6.27 ppm (triplet, para). Figure 1 shows the H NMR
spectrum of 11 and its assignment. The corresponding
mononuclear complex [(2,6-iPr2C6H3)-NdCH-(2-anthra-
cenyl-C6H3-O)-κ2-N,O]Ni(η3-CH2Ph) (13) is prepared by
a similar method as a comparison catalyst for the
polymerization studies. Grubbs reported preparation of

Macromolecules, Vol. 38, No. 24, 2005
Ethylene/Polar Norbornene Copolymerizations 10029
Figure 1. 1H NMR spectrum of 11.
Table 1. Ethylene Polymerization Resultsa
activity (kg/
entry
catalyst
temp (°C)b
(mol of Ni h))
Tm (°C)
Mw
Mw/Mn
branchesc
16
1
10
11
11
12
13e
13
45-59
45-84
45-62
45-59
45-89
45-62
1900
3000
2400
2100
2300
2400
122
44 000
28 000
55 000
50 000
37 000
72 000
3.0
16
3.6
3.5
15
2
3d
4
114 (94)
117
51
45
5
6d
120
4.2
23
a Polymerization conditions: 30 mL of toluene, 5 µmol of Ni, 100 psig of ethylene, 10 min. b Initial temperature - final temperature.
c Determined by the 1H NMR and corresponds to the number of branches/1000 carbons. d 5 min of polymerization time. e Mononuclear
complex, [(2,6-iPr2C6H3)-NdCH-(2-anthracenyl-C6H3-O)-κ2-N,O]Ni(η3-CH2Ph).
Table 2. Ethylene/2-(Methoxycarbonyl)norbornene
Copolymerization Resultsa
activity (kg/
(mol of Ni h))
b
c
entry catalyst fM
FM
Mw
Mw/Mn
1
2
3
4
5
6
7
8
10
10
10
10
11
11
11
11
12
12
12
12
13d
13
13
13
0.11 0.12
0.20 0.17
0.27 0.20
0.33 0.27
0.11 0.12
0.20 0.18
0.27 0.22
0.33 0.29
0.11 0.14
0.20 0.20
0.27 0.26
0.33 0.42
0.11 0.076
0.20 0.099
0.27 0.12
0.33 0.15
110
80
61
59
100
72
60
58
110
69
61
58
83
41
36
33
31 000
52 000
30 000
17 000
48 000
28 000
18 000
15 000
39 000
52 000
35 000
18 000
54 000
31 000
31 000
29 000
3.6
4.5
3.7
2.7
3.7
3.8
4.2
3.2
3.6
5.1
4.1
2.9
4.2
4.2
4.0
4.5
9
10
11
12
13
14
15
16
Figure 2. Relationship between the 2-(methoxycarbonyl)-
norbornene mole fraction in the monomer feeding (fM) and that
in the copolymers (FM) prepared from 10-13.
a Polymerization conditions: 30 mL of toluene solution of
2-(methoxycarbonyl)norbornene (0.075, 0.15, 0.22, and 0.30 M),
20 µmol of Ni, 100 psig of ethylene (0.60 M), 45 °C, 15 min. b 2-
(Methoxycarbonyl)norbornene mole fraction in the monomer feed-
ing. c 2-(Methoxycarbonyl)norbornene mole fraction in the copoly-
mer determined by the 1H NMR. d Mononuclear complex, [(2,6-
iPr2C6H3)-NdCH-(2-anthracenyl-C6H3-O)-κ2-N,O]Ni(η3-CH2Ph).
Among the three dinuclear complexes, ortho-C6H4-
(C6H4)2-bridged complex 12 exhibits the highest incor-
poration of the polar monomer (entries 9-12), and the
mole fraction of 2-(methoxycarbonyl)norbornene in the
copolymer is ∼2 times higher than that observed for the
copolymer obtained by the mononuclear complex 13
under the same monomer feed ratio (entries 13-16).
Figure 2 shows the relationship between the 2-(meth-
oxycarbonyl)norbornene mole fraction in the polymer
(FM) and that in the monomer feeding (fM). Almost linear
relationships between FM and fM are observed for all
complexes, except the point at fM ) 0.33 of complex 12.
An attempt to evaluate the monomer reactivity ratio r1
and r2 by fitting the (fA, FA) data set to the Fineman-
Ross plot is unsuccessful.17 A straight line is not
obtained at all in all cases.
by the bimetallic complexes 10-12 are slightly lower
than that observed for the polymer obtained by the
mononuclear complex 13.
Some dramatic effects of the dinuclearity are observed
in the ethylene/functionalized norbornene copolymeriza-
tions (eq 3).16 The dinuclear complexes 10-12 show ∼2
times higher activities than the mononuclear complex
13 under the same conditions in ethylene/2-(methoxy-
carbonyl)norbornene copolymerizations (Table 2). As
expected, the dinuclear complexes exhibit much higher
incorporation of 2-(methoxycarbonyl)norbornene under
the same monomer feed ratio (Table 2 and Figure 2).

10030 S et al.
Macromolecules, Vol. 38, No. 24, 2005
Table 3. Ethylene/2-(Acetoxymethyl)norbornene
Copolymerization Resultsa
activity (kg/
(mol of Ni h))
b
c
entry catalyst fA
FA
Mw
Mw/Mn
1
10
10
10
10
11
11
11
11
12
12
12
12
13d
13
13
13
0.33 0.064
0.43 0.094
0.50 0.11
0.56 0.13
0.33 0.071
0.43 0.11
0.50 0.14
0.56 0.17
0.33 0.099
0.43 0.12
0.50 0.16
0.56 0.19
0.33 0.029
0.43 0.040
0.50 0.052
0.56 0.070
59
40
32
31
61
41
31
28
61
43
35
29
24
16
15
14
27 000
22 000
22 000
20 000
27 000
22 000
17 000
22 000
30 000
30 000
24 000
20 000
22 000
20 000
18 000
22 000
2.7
2.6
2.4
2.0
2.6
2.9
2.2
2.3
2.6
2.6
2.2
2.5
2.3
2.4
2.7
2.1
2
3
Higher activities and higher incorporations of polar
norbornene are also observed for ethylene/2-(acetoxy-
methyl)norbornene copolymerizations (Table 3). Incor-
poration of 2-(acetoxymethyl)norbornene is much more
difficult than that of 2-(methoxycarbonyl)norbornene,
and thus higher feeding of the 2-(acetoxymethyl)nor-
bornene is required to obtain a copolymer having similar
composition. The order of the polar norbornene incor-
poration ability observed for ethylene/2-(acetoxymethyl)-
norbornene copolymerizations is the same with that
observed for the ethylene/2-(methoxycarbonyl)norbornene
copolymerizations: 12 > 11 > 10 > 13. The effect of
dinuclearity is more dramatic in the ethylene/2-(ac-
etoxymethyl)norbornene copolymerizations, and com-
plex 12 shows almost 3 times higher incorporations of
the 2-(acetoxymethyl)norbornene than the mononuclear
complex 13 under the same feed ratio. Figure 3 shows
the relationship between the 2-(acetoxymethyl)nor-
bornene mole fraction in the polymer (FA) and that in
the monomer feeding (fA). In the cases of 10 and 11, an
almost perfect linear relationship (R values, 0.9972 and
0.9996 for 10 and 11, respectively) is observed with the
steeper slope for complex 11. In the case of 12, three
points except the point at fA ) 0.33 exhibit a linear
relationship. The (fA, FA) data set for each complex does
not give straight lines in the Fineman-Ross plot.
Narrow molecular weight distributions (Mw/Mn, 2.1-
2.9) are observed, indicating a single active species, and
the molecular weights are not sensitive to the bridge
structure (Mw, 20 000-30 000).
4
5
6
7
8
9
10
11
12
13
14
15
16
a Polymerization conditions: 30 mL of toluene solution of
2-(acetoxymethyl)norbornene (0.30, 0.45, 0.60, and 0.75 M), 20
µmol of Ni, 100 psig of ethylene (0.60 M), 45 °C, 15 min.
b 2-(Acetoxymethyl)norbornene mole fraction in the monomer
feeding. c 2-(Acetoxymethyl)norbornene mole fraction in the co-
polymer determined by the 1H NMR. d Mononuclear complex, [(2,6-
iPr2C6H3)-NdCH-(2-anthracenyl-C6H3-O)-κ2-N,O]Ni(η3-CH2Ph).
Theoretical Calculations. Geometry optimizations
on the active species derived from complexes 10-12
were performed with Hartree-Fock theory to see
whether the bimetallic mechanism proposed in eq 1 is
fit for the complexes. The complexes were simplified by
removing the anthracenyl groups and replacing the η3-
benzyl ligands with methyls, and full geometry optimi-
zations were conducted on the initial structures where
the carbonyl oxygen of the endo-2-(acetoxymethyl)-
nobornene monomer was placed near a nickel center
while the other nickel center is kept vacant. The
optimized structures are shown in Figure 4. In all the
three structures, the two metals are situated opposite
each other, and the double bond on the norbornyl unit
is directed toward the vacant site on the other nickel
center, consequently supporting the possibility for the
bimetallic mechanism proposed in eq 1. The Ni-Ni
separation increases in the order of 10 (6.241 Å) < 12
(7.352 Å) < 11 (9.404 Å). The separation between the
norbornyl double bond and the nickel center increases
in the same order: 10 (the C-Ni distances, 2.469 and
2.544 Å) < 12 (the C-Ni distances, 3.563 and 3.813 Å)
< 11 (the C-Ni distances, 5.668 and 6.753 Å). Because
the double bond is situated more proximal to the nickel
center for the structure derived from 12 than for the
structure derived from 11, the binding mode change
from the oxygen to the double bond proposed in eq 1 is
better expected for 12, possibly leading to higher
incorporation of the polar monomer with 12, which is
in agreement with the experimental results. An efficient
binding mode change and consequently much higher
Figure 3. Relationship between the 2-(acetoxymethyl)-
nobornene mole fractions in the monomer feeding (fA) and that
in the copolymers (FA) prepared from 10-13.
Figure 4. Calculated structures of endo-2-(acetoxymethyl)-
nobornene coordinated active species derived from complexes
10-12. Anthracenyl fragments are removed and the η3-benzyl
ligands are replaced with methyls for simplicity.
incorporation of the polar monomer can be expected for
10 because the separation between the nickel center and
the double bond is the shortest for the structure derived
from 10, but the lowest incorporation of the polar
monomer is observed with 10. This discrepancy might
be explained by too short Ni-Ni separations. In the
structure of 10, there is not enough space between the
nickels, and there may be severe steric repulsion when
the methyl attached on the nickel is replaced with the

Macromolecules, Vol. 38, No. 24, 2005
Ethylene/Polar Norbornene Copolymerizations 10031
Compound 4. Compound 1 (0.20 g, 0.47 mmol), 3-anthra-
cenylsalicylaldehyde (0.35 g, 1.17 mmol), and p-toluenesulfonic
acid (0.005 g, 0.0234 mmol) were added into a flask (50 mL),
and benzene (8 mL) was added. The flask was connected to a
Dean-Stark apparatus, and the solution was refluxed over-
night. After the solution was cooled to room temperature,
solvent was removed by rotary evaporator to give a residue
which was triturated in hexane for 5 h. Yield was 0.422 g
(91%); mp 228 °C. IR (KBr): 3413 (OH) and 1630 cm-1 (Cd
actual norbornyl group. In the structure derived from
10, the separation between the two methyls is 4.637 Å,
which implies that even the two methyls are situated
almost in van der Waals contact.
Summary. Dinuclear salicylaldimine neutral-nickel-
(II) complexes 10-12 with various bridge units are
prepared (Scheme 1). Some dinuclear effects are ob-
served in the ethylene homopolymerization and ethyl-
ene/functionalized norbornene copolymerizations. In the
ethylene polymerization, higher branches are observed
with methylene-bridged complex 11. In the ethylene/2-
(methoxycarbonyl)norbornene and in the ethylene/2-
(acetoxymethyl)norbornene copolymerizations, the di-
nuclear complexes 10-12 show higher activities and
higher polar norbornene incorporations than the mono-
nuclear complex 13. The polar norbornene incorporation
is also dependent on the bridge structure, and the C6H4-
(C6H4)2-bridged complex 12 shows the highest incorpo-
ration of the polar norbornenes in both copolymeriza-
tions. We assume that the higher incorporations of the
polar norbornenes are attributed to the cooperative
action between the two metal centers.
1
N). H NMR (CDCl3): δ 1.04 (d, J ) 7.2 Hz, 12H, CH3), 2.98
(septet, J ) 7.2 Hz, 2H, CH), 6.98 (s, 2H, iPr2C6-H), 7.21 (t, J
) 7.2 Hz, 1H, phenol-pH), 7.36-7.64 (m, 8H), 7.80 (d, J ) 8.4
Hz, 2H, anthracenyl-H), 8.11 (d, J ) 8.4 Hz, 2H, anthracenyl-
H), 8.40 (s, 1H, anthracenyl-H10 or NdCH), 8.59 ppm (s, 1H,
anthracenyl-H10 or NdCH). 13C{1H} NMR (CDCl3): δ 23.76
(CH3), 27.90 (CH), 118.69, 118.78, 124.94, 125.03, 125.41,
126.36, 126.66, 126.98, 127.20, 128.45, 129.83, 130.15, 131.31,
132.04, 132.22, 136.43, 138.19, 138.37, 140.98, 144.23, 159.15,
166.47 ppm. Anal. Calcd (C72H64N2O2): C, 87.41; H, 6.52; N,
2.83. Found: C, 87.25; H, 6.83; N, 3.11%.
Compound 5. The compound was synthesized according
to same conditions and procedure as for 4 using 2. Yield was
57%; mp 209 °C. IR (KBr): 3401 (OH) and 1631 cm-1 (CdN).
1H NMR (CDCl3): δ 1.18 (d, J ) 7.2 Hz, 12H, CH3), 3.05
(septet, J ) 7.2 Hz, 2H, CH), 4.02 (s, 1H, CH2), 7.03 (s, 2H,
iPr2C6-H), 7.21 (t, J ) 7.2 Hz, 1H, phenol-pH), 7.38-7.56 (m,
7H), 7.61 (d, J ) 7.2 Hz, 1H, phenol-mH), 7.79 (d, J ) 8.4 Hz,
2H, anthracenyl-H), 8.09 (d, J ) 8.4 Hz, 2H, anthracenyl-H),
8.49 (s, 1H, anthracenyl-H10 or NdCH), 8.56 ppm (s, 1H,
antracenyl-H10 or NdCH). 13C{1H} NMR (CDCl3): δ 23.82
(CH3), 28.14 (CH), 29.81 (CH2), 118.72, 118.78, 123.65, 124.94,
125.41, 126.39, 126.70, 127.01, 128.46, 130.17, 131.34, 132.00,
132.11, 136.50, 137.71, 138.73, 143.81, 159.26, 166.51 ppm.
Anal. Calcd (C79H70N2O2): C, 87.90; H, 6.54; N, 2.60. Found:
C, 88.23; H, 6.66; N, 2.59%.
Experimental Section
All manipulations were performed under an inert atmo-
sphere using standard glovebox and Schlenk techniques.
Toluene, pentane, THF, and C6D6 were distilled from ben-
zophenone ketyl. 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 several days under the pressure of 200 psig.
2-(Acetoxymethyl)norbornene was prepared according to the
1
literature method.18 The H NMR (400 MHz), 13C NMR (100
Compound 6. The compound was synthesized according
to the same conditions and procedure as for 4 using 3. Yield
was 92%; mp 222 °C. IR (KBr): 3394 (OH) and 1634 cm-1 (Cd
MHz), and 31P NMR (162 MHz) spectra were recorded on a
Varian Mercury plus 400. Elemental analyses were carried
out at the Inter-University Center Natural Science Facilities,
Seoul National University. Gel permeation chromatograms
(GPC) were obtained at 140 °C in trichlorobenzene using a
Waters model 150-C+ GPC, and the data were analyzed using
a polystyrene analyzing curve. Differential scanning calorim-
etry (DSC) was performed on a Thermal Analysis 3100.
Compound 3. The boronic acid (2.60 g, 6.75 mmol), Na2-
CO3 (1.95 g, 10.2 mmol), Pd(PPh3)4 (0.10 g, 0.068 mmol), and
4,4′-dibromoterphenyl were added into a Schlenk flask inside
a glovebox. The flask was brought out, and degassed DME (35
mL) and water (10 mL) were added. The flask was sealed with
screw-cap and heated at 100 °C overnight. The solution was
cooled to room temperature, and the organic phase was
extracted with ethyl acetate. Solvent was removed by rotary
evaporator to give a residue which was purified by column
chromatography on silica gel eluting with hexane and ethyl
acetate (10:1). The obtained solid was dissolved in THF (22
mL), and aqueous HCl (2 N, 11 mL) was added. After the
solution was stirred at 60 °C for 2 h, solvent was removed by
a rotary evaporator. White solid was thoroughly washed with
diethyl ether until benzophenone is not detected in the ethereal
solution. To a flask containing the white solid, diethyl ether
(30 mL) and aqueous KOH solution (1.0 N, 35 mL) were added.
Ethereal phases were collected, and the water phase was
extracted with additional diethyl ether (30 mL). The ethereal
phase was combined and dried over anhydrous MgSO4. Solvent
was removed with rotary evaporator to give a white crystalline
1
N). H NMR (CDCl3): δ 1.23 (d, J ) 6.8 Hz, 12H, CH3), 3.08
(septet, J ) 6.8 Hz, 2H, CH), 7.23 (t, J ) 7.6 Hz, 1H, phenol-
pH), 7.27 (s, 2H, iPr2C6-H), 7.29 (d, J ) 8 Hz, 2H, C6H4-H),
7.34-7.60 (m, 9H), 7.64 (d, J ) 7.2 Hz, 1H, phenol-mH), 7.77
(d, J ) 8.4 Hz, 2H, anthracenyl-H), 8.09 (d, J ) 8.4 Hz, 2H,
anthracenyl-H), 8.50 (s, 1H, anthracenyl-H10 or NdCH),
8.56 ppm (s, 1H, anthracenyl-H10 or NdCH). 13C{1H}
NMR (CDCl3): δ 23.84 (CH3), 28.31 (CH), 118.72, 118.84,
121.88, 124.95, 125.42, 126.36, 126.76, 127.02, 127.45, 128.47,
130.15, 130.57, 131.32, 131.99, 132.20, 136.57, 137.50, 139.16,
139.91, 140.05, 145.34, 159.24, 166.55 ppm. Anal. Calcd
(C84H72N2O2): C, 88.38; H, 6.36; N, 2.45. Found: C, 88.25; H,
6.52; N, 2.54%.
Compound 7. To a flask containing compound 4 (0.200 g,
0.202 mmol) in THF (2 mL) was added KH (0.17 g, 0.44 mmol),
and the solution was stirred overnight. The solution was
filtered, and solvent was removed under vacuum to give a
yellow residue. To a flask containing the residue was added a
solution of (η3-CH2C6H5)NiCl(PMe3) (0.218 g, 0.202 mmol) in
toluene (4 mL). After the resulting solution was stirred for 1.5
h at room temperature, it was filtered over Celite, and solvent
was removed under vacuum to yield a light brown powder. In
case that THF signals were observed in the NMR spectra, the
complex was dissolved in a minimum amount of toluene and
then evacuated once again to remove the residual THF. THF
should be completely removed for the next reaction. Yield was
1
2
0.244 g (76%). H NMR (C6D6): δ -0.20 (d, JPH ) 10 Hz, 9H,
1
3
solid which was pure by the analysis of the H and 13C NMR
PMe3), 0.90 (d, JPH ) 7.2 Hz, 2H, benzyl-CH2), 1.07 (d, J )
spectra, and it was used for the next reaction without further
purification. Yield was 1.04 g (59%); mp 245 °C. IR (KBr): 3491
6.8 Hz, 6H, CH3), 1.23 (d, J ) 6.8 Hz, 6H, CH3), 4.29 (septet,
J ) 6.8 Hz, 2H, CH), 6.77 (t, J ) 7.6 Hz, 1H, phenol-pH), 6.97
(t, J ) 7.2 Hz, 1H, benzyl-pH), 7.04 (t, J ) 7.2 Hz, 2H, benzyl-
mH), 7.07 (s, 2H, iPr2C6-H), 7.09-7.26 (m, 5H), 7.27 (dd, J )
7.6, 2.0 Hz, 1H, phenol-mH), 7.33 (AA′BB′, C6H4-H), 7.38 (dd,
J ) 6.8, 1.6 Hz, 1H, phenol-mH), 7.80 (d, J ) 7.6 Hz, 2H,
benzyl-oH), 7.84 (d, J ) 8.4 Hz, 2H, anthracenyl-H), 8.03 (d,
1
and 3401 cm-1 (N-H). H NMR (CDCl3): δ 1.40 (d, J ) 7.2
Hz, 12H, CH3), 3.05 (septet, J ) 7.2 Hz, 2H, CH), 3.99 (br s,
2H, NH), 7.28-7.64 ppm (m, 8H). 13C{1H} NMR (CDCl3): δ
22.58 (CH3), 28.12 (CH), 121.31, 125.79, 127.17, 129.94, 130.49,
130.59, 132.59, 139.04, 139.39, 139.74, 140.02 ppm. Anal.
Calcd (C42H48N2): C, 86.85; H, 8.33; N, 4.82%. Found: C, 86.79;
H, 8.31; N 4.78, %.
4
J ) 8.4 Hz, 2H, anthracenyl-H), 8.14 (d, JPH ) 8.4 Hz, 1H,
NdCH), 8.20 ppm (s, 1H, anthracenyl-H10). 13C{1H} NMR

10032 S et al.
Macromolecules, Vol. 38, No. 24, 2005
2
1
(C6D6): δ 8.59 (d, JPC ) 33.4 Hz, benzyl-CH2), 11.08 (d, JPC
) 25.8 Hz, PMe3), 23.89 (CH3), 25.62 (CH3), 28.90 (CH), 114.21,
120.37, 123.42, 125.22, 125.28, 125.54, 125.86, 127.49, 127.64,
128.17, 128.54, 129.61, 130.91, 131.26, 131.85, 131.99, 134.52,
136.81, 137.05, 140.20, 141.27, 141.48, 147.93, 150.29, 165.52
ppm. 31P{1H} NMR (C6D6): δ 5.35 ppm. Anal. Calcd (C92H94N2-
Ni2O2P2): C, 76.78; H, 6.58; N, 1.95. Found: C, 76.92; H, 6.85;
N, 2.25%.
J ) 7.2, 1.2 Hz, 1H, phenol-mH), 7.67 (s, 1H, NdCH), 7.76 (d,
J ) 8.4 Hz, 2H, anthracenyl-H), 7.90 (d, J ) 8.4 Hz, 2H,
anthracenyl-H), 8.31 ppm (s, 1H, anthracenyl-H10). 13C{1H}
NMR (C6D6): δ 23.34 (CH3), 25.46 (CH3), 27.87 (CH), 28.55
(benzyl-CH2), 42.09(CH2), 106.73, 114.20, 116.15, 119.41,
124.02, 124.90, 125.17, 125.65, 125.93, 125.82, 128.44, 131.23,
131.73, 131.97, 133.80, 134.47, 136.48, 136.94, 138.95, 139.95,
150.77, 164.77, 165.12 ppm.
Compound 8. The compound was synthesized according
to the same conditions and procedure as for 7 using 5. Yield
Compound 12. The compound was synthesized according
to the same conditions and procedure as for 10 using 9. Yield
was 74%. 1H NMR (C6D6): δ 0.70 (s, 2H, benzyl-CH2), 0.95 (d,
J ) 6.8 Hz, 6H, CH3), 1.20 (d, J ) 6.8 Hz, 6H, CH3), 3.79
(septet, J ) 6.8 Hz, 2H, CH), 6.03 (t, J ) 7.6 Hz, 2H, benzyl-
mH), 6.18 (d, J ) 6.8 Hz, 2H, benzyl-oH), 6.28 (t, J ) 7.2 Hz,
1H, benzyl-pH), 6.59 (t, J ) 7.2 Hz, 1H, phenol-pH), 6.92 (t, J
) 6.4 Hz 2H, anthracenyl-H), 7.18-7.40 (m, 10H), 7.46 (t, J
) 6.4, 2H, anthracenyl-H), 7.74 (d, J ) 4.8 Hz, 2H, anthra-
cenyl-H), 7.76 (s, 1H, NdCH), 7.90 (d, J ) 8.4 Hz, 2H,
anthracenyl-H), 8.31 ppm (s, 1H, anthracenyl-H10). 13C{1H}
NMR (C6D6): δ 23.02 (CH3), 25.20 (CH3), 27.92 (CH), 28.50
(benzyl -CH2), 106.60, 114.09, 115.97, 119.22, 122.26, 124.73,
125.02, 125.79, 126.70, 127.06, 127.60, 128.84, 130.66, 130.87,
131.08, 131.58, 131.68, 131.83, 133.62, 134.31, 136.29, 136.85,
138.54, 139.89, 140.14, 140.39, 140.87, 151.64, 164.46, 165.07
ppm.
2
was 80%. 1H NMR (C6D6): δ -0.22 (d, JPH ) 10.4 Hz, 9H,
3
PMe3), 0.89 (d, JPH ) 6.0 Hz, 2H, benzyl-CH2), 1.13 (d, J )
6
6.8 Hz, H, CH3), 1.27 (d, J ) 6.8 Hz, 6H, CH3), 3.82 (s, 1H,
CH2), 4.24 (septet, J ) 6.8 Hz, 2H, CH), 6.69 (t, J ) 6.8 Hz,
1H, phenol-pH), 6.93 (t, J ) 7.2 Hz, 1H, benzyl-pH), 7.01 (s,
2H, iPr2C6-H), 7.96-7.28 (m, 7H), 7.33 (dd, J ) 6.8, 1H,
phenol-mH), 7.77 (d, J ) 7.2 Hz, 2H, benzyl-oH), 7.82 (d, J )
8.4 Hz, 2H, anthracenyl-H), 8.01 (d, J ) 8.4 Hz, 3H, NdCH
and anthracenyl-H), 8.19 ppm (s, 1H, anthracenyl-H10). 13C-
{1H} NMR (C6D6): δ 8.58 (d, 2JPC ) 33.4 Hz, benzyl-CH2), 11.05
(d, 1JPC ) 25.8 Hz, PMe3), 22.91 (CH3), 23.82 (CH3), 25.42 (CH),
28.94 (CH2), 113.98, 120.30, 123.33, 124.19, 125.17, 125.25,
125.65, 125.81, 127.51, 128.51, 129.27, 129.67, 131.24, 131.68,
131.97, 134.43, 136.64, 137.11, 139.14, 141.69, 147.48, 150.47,
165.42 ppm. 31P{1H} NMR (C6D6): δ 5.06 ppm. Anal. Calcd
(C87H92N2Ni2O2P2): C, 75.88; H, 6.73; N, 2.03. Found: C, 76.21;
H, 6.95; N, 2.10%.
Compound 13. The η1-benzyl PMe3 nickel(II) complex was
synthesized according to the same conditions and procedure
as for 7 using 2-anthracen-9-yl-6-[(2,6-diisopropylphenyl)-
iminomethyl]phenol. Yield was 96%. Data for the η1-benzyl
Compound 9. The compound was synthesized according
to the same conditions and procedure as for 7 using 6. Yield
2
was 73%. 1H NMR (C6D6): δ -0.27 (d, JPH ) 9.6 Hz, 9H,
PMe3 nickel(II) complex: 1H NMR (C6D6): δ -0.28 (d, 2JPH
)
3
3
PMe3), 0.84 (d, JPH ) 6.0 Hz, 2H, benzyl-CH2), 1.07 (d, J )
10.0 Hz, 9H, PMe3), 0.80 (d, JPH ) 6.0 Hz, 2H, benzyl-CH2),
1.10 (d, J ) 7.2 Hz, 6H, CH3), 1.22 (d, J ) 7.2 Hz, 6H, CH3),
4.23 (septet, J ) 7.2 Hz, 2H, CH), 6.66 (t, J ) 7.2 Hz, 1H,
phenol-pH), 6.88 (t, J ) 7.6 Hz, 1H, benzyl-pH), 6.94 (t, J )
7.6 Hz, 2H, benzyl-mH) 6.98-7.24 (m, 8H), 7.29 (dd, J ) 6.8,
1.6 Hz, 1H, phenol-mH), 7.70 (d, J ) 7.2 Hz, 2H, benzyl-oH),
7.78 (d, J ) 8.0 Hz, 2H, anthracenyl-H), 7.97 (d, J ) 8.0 Hz,
2H, anthracenyl-H), 8.03 (d, 4JPH ) 8.4 Hz, 1H, NdCH), 8.15
ppm (s, 1H, anthracenyl-H10). 13C{1H} NMR (C6D6): δ 8.30 (d,
2JPC ) 33.3 Hz, benzyl-CH2), 11.07 (d, 1JPC ) 25.8 Hz, PMe3),
23.71, 25.40, 28.90, 114.02, 120.24, 123.05, 123.36, 123.69,
125.18, 125.24, 125.81, 126.63, 127.54, 128.12, 128.41, 129.62,
131.25, 131.72, 131.97, 134.42, 136.71, 137.08, 141.61, 149.42,
150.40 (d, J ) 4.6 Hz), 165.39 ppm (d, J ) 15.2 Hz). 31P{1H}
NMR (C6D6): δ 5.15 ppm. Anal. Calcd (C43H46NOPNi): C,
75.67; H, 6.79; N, 2.05%. Found: C, 75.95; H, 6.82; N, 2.42%.
The PMe3-free η3-benzyl-nickel(II) complex 13 was synthe-
sized according to the same conditions and procedure as for
10 from the η1-benzyl-PMe3-nickel(II) complex. Data for 13:
1H NMR (C6D6): δ 0.74 (s, 2H, benzyl-CH2), 0.99 (d, J ) 6.8
Hz, 6H, CH3), 1.25 (d, J ) 6.8 Hz, 6H, CH3), 3.81 (septet, J )
7.2 Hz, 2H, CH), 6.09 (t, J ) 7.6 Hz, 2H, benzyl-mH), 6.20 (d,
J ) 7.6 Hz, 2H, benzyl-oH), 6.32 (t, J ) 7.6 Hz, 1H, benzyl-
pH), 6.62 (t, J ) 6.8 Hz, 1H, phenol-pH), 6.96 (t, J ) 6.8 Hz,
2H, anthracenyl-H), 7.00-7.08 (m, 3H, iPr2C6-H), 7.10 (dd,
J ) 7.2, 1.2 Hz, 1H, phenol-mH), 7.25 (t, J ) 6.8 Hz, 2H,
anthracenyl-H), 7.33 (dd, J ) 7.2, 1.2 Hz, 1H, phenol-mH),
7.74 (s, 1H, NdCH), 7.83 (d, J ) 8.8 Hz, 2H, anthracenyl-H),
7.95 (d, J ) 8.8 Hz, 2H, anthracenyl-H), 8.35 ppm (s, 1H,
anthracenyl-H10). 13C{1H} NMR (C6D6): δ 23.23, 25.41, 28.49,
106.67, 114.12, 116.12, 119.33, 123.58, 124.84, 125.15, 125.89,
126.34, 126.82, 128.52, 131.27, 131.80, 132.00, 133.79, 134.26,
134.46, 136.59, 136.89, 139.77, 152.41, 164.54, 165.19 ppm.
Polymerization. To a 60 mL glass reactor containing a
stirring bar was added toluene or toluene solution of the
functionalized norbornene (30 mL). The reactor was assembled
and brought out of the glovebox. The reactor was immersed
in an oil bath, the temperature of which had been set to 45
°C. The solution was stirred until the temperature reached
that of the oil bath. The nickel complex dissolved in toluene
(2 mL) was injected to the reactor via a syringe, and ethylene
was fed continuously for a given time under the pressure of
100 psig. The temperature of the solution was monitored. In
the ethylene polymerization, the oil bath was replaced with
an ice bath right after the ethylene charge. After release of
6.8 Hz, 6H, CH3), 1.18 (d, J ) 6.8 Hz, 6H, CH3), 4.25 (septet,
J ) 6.8 Hz, 2H, CH), 6.68 (t, J ) 7.2 Hz, 1H, phenol-pH), 6.88
(t, J ) 6.8 Hz, 1H, benzyl-pH), 6.95 (t, J ) 6.8 Hz, 2H, benzyl-
mH), 7.01-7.47 (m, 8H), 7.11 (s, 2H, iPr2C6-H), 7.70 (d, J )
6.8 Hz, 2H, benzyl-oH), 7.78 (d, J ) 8.4 Hz, 2H, anthracenyl-
4
H), 7.97 (d, J ) 8.4 Hz, 2H, anthracenyl-H), 8.04 (d, JPH
)
8.4 Hz, 1H, NdCH), 8.15 ppm (s, 1H, anthracenyl-H10). 13C-
{1H} NMR (C6D6): δ 8.34 (d, 2JPC ) 33.3 Hz, benzyl-CH2), 10.90
(d, 1JPC ) 26.6 Hz, PMe3), 23.50 (CH3), 25.20 (CH3), 28.93 (CH),
113.94, 120.12, 122.45, 123.23, 125.05, 125.11, 125.50, 125.69,
127.11, 127.42, 127.98, 128.36, 129.12, 129.51, 130.54, 131.10,
131.64, 131.82, 134.28, 136.63, 136.88, 137.65, 138.86, 139.99,
140.47, 140.72, 141.97, 145.75, 150.19 (J ) 4.5 Hz), 165.28 (J
) 12.9 Hz) ppm. 31P{1H} NMR (C6D6): δ 5.32 ppm. Anal. Calcd
(C104H102N2Ni2O2P2): C, 78.50; H, 6.46; N, 1.76. Found: C,
78.35; H, 6.65; N, 1.90%.
Compound 10. To a flask containing compound 7 (0.132
g, 0.096 mmol) and B(C6F5)3 (0.103 g, 0.201 mmol) was added
toluene (2 mL) at room temperature. The solution was stirred
for 1.5 h. The white precipitates of B(C6F5)3‚PMe3 were
removed by filtration. Solvent was removed to give red powder
which was pure by the analysis of the 1H and 13C NMR spectra.
Yield was 0.097 g (77%). 1H NMR (C6D6): δ 0.78 (s, 2H, benzyl-
CH2), 0.89 (d, J ) 6.8 Hz, 6H, CH3), 1.19 (d, J ) 6.8 Hz, 6H,
CH3), 3.76 (septet, J ) 6.8 Hz, 2H, CH), 6.03 (t, J ) 7.6 Hz,
2H, benzyl-mH), 6.18 (d, J ) 7.6 Hz, 2H, benzyl-oH), 6.27 (t,
J ) 8.4 Hz, 1H, benzyl-pH), 6.62 (t, J ) 7.6 Hz, 1H, phenol-
pH), 7.00 (s, 2H, iPr2C6-H), 6.84-7.26 (m, 6H), 7.30 (d, J )
6.0 Hz, 1H, phenol-mH), 7.42 (AA′BB′, C6H4-H), 7.77 (d, J
) 8.4 Hz, 2H, anthracenyl-H), 7.85 (s, 1H, NdCH), 7.90 (d, J
) 8.4 Hz, 2H, anthracenyl-H), 8.31 ppm (s, 1H, anthracenyl-
H10). 13C{1H} NMR (C6D6): δ 23.33 (CH3), 25.78 (CH3), 28.23
(CH), 28.45 (benzyl -CH2), 106.77, 114.43, 116.14, 119.39,
124.94, 125.20, 125.32, 125.65, 126.00, 126.89, 128.51, 129.27,
130.89, 131.25, 131.76, 131.98, 133.70, 134.53, 136.38, 137.08,
139.66, 140.00, 141.36, 150.80, 164.63, 165.25 ppm.
Compound 11. The compound was synthesized according
to the same conditions and procedure as for 10 using 8. Yield
was 73%. 1H NMR (C6D6): δ 0.76 (s, 2H, benzyl-CH2), 0.97 (d,
J ) 6.8 Hz, 6H, CH3), 1.25 (d, J ) 6.8 Hz, 6H, CH3), 3.78
(septet, J ) 6.8 Hz, 2H, CH), 3.91 (s, 1H, CH2), 6.02 (t, J )
7.6 Hz, 2H, benzyl-mH), 6.18 (d, J ) 7.6 Hz, 2H, benzyl-oH),
6.26 (t, J ) 7.6 Hz, 1H, benzyl-pH), 6.56 (t, J ) 6.8 Hz, 1H,
phenol-pH), 7.02 (s, 2H, iPr2C6-H), 6.86-7.24 (m, 5H), 7.26 (dd,

Macromolecules, Vol. 38, No. 24, 2005
Ethylene/Polar Norbornene Copolymerizations 10033
(6) (a) Jenkins, J. C.; Brookhart, M. J. Am. Chem. Soc. 2004,
126, 5827. (b) Mu¨ller, C.; Ackerman, L. J.; Reek, J. N. H.;
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J. C.; Brookhart, M. Organometallics 2003, 22, 3533. (f)
Zhang, D.; Jin, G.-X. Organometallics 2003, 22, 2851.
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ethylene pressure, acetone (60 mL) was added to the reactor
to obtain white precipitates, which were collected by filtration
and dried under vacuum. In the case of ethylene/functionalized
norbornene copolymerizations, solvent was removed under
vacuum and methanol (20 mL) and a few drops of HCl were
added. The solution was stirred for 30 min to obtain white
precipitates, which were filtered and washed with methanol
(50 mL). The mole fractions in the ethylene/functionalized
norbornene copolymers were calculated by the analysis of the
1H NMR spectra. Branch numbers of the polyethylenes were
calculated from the integration value of methyl, methylene,
and methine proton regions in the 1H NMR spectra. The NMR
spectra of the polyethylene were obtained at 100 °C in benzene-
d6 and 1,2,4-trichlorobenzene (v/v, 4:1). The NMR spectra of
the ethylene/functionalized norbornene copolymers were ob-
tained at 70 °C in benzene-d6. Ethylene concentration in
toluene at 45 °C (0.60 M) was measured with mass flow
controller.
Theoretical Calculations. Geometry optimizations were
performed with Hartree-Fock theory in combination with the
3-21G basis set. The GAMESS (general atomic and molecular
electronic structure system) program was used for the com-
putations.19
(10) Guo, N.; Li, L.; Marks, T. J. J. Am. Chem. Soc. 2004, 126,
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S. O. Organometallics 2004, 23, 5382.
Acknowledgment. This work was supported by
Korea Research Foundation Grant funded by Korea
Government (MOEHRD, Basic Reasearch Promotion
Fund) (KRF-2005-015-C00233).
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References and Notes
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(2) Review for the late transition metal catalysts: (a) Gibson,
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