Syntheses, structures and catalytic activity of copper(II) complexes with hydroxyindanimine ligands

Article abstract of DOI:10.1016/j.jorganchem.2007.06.023

A series of new hydroxyindanimine ligands [ArN{double bond, long}CC₂H₃(CH₃)C₆H₂(R)OH] (Ar = 2,6-i-Pr₂C₆H₃, R = H (HL¹), R = Cl (HL²), and R = Me

Full text of DOI:10.1016/j.jorganchem.2007.06.023

Journal of Organometallic Chemistry 692 (2007) 4106–4112
www.elsevier.com/locate/jorganchem
Syntheses, structures and catalytic activity of copper(II) complexes
with hydroxyindanimine ligands
*
Guangrong Tang, Yue-Jian Lin, Guo-Xin Jin
Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai 200433, PR China
Received 23 April 2007; received in revised form 6 June 2007; accepted 12 June 2007
Available online 23 June 2007
Abstract
A series of new hydroxyindanimine ligands [ArN@CC2H3(CH3)C6H2(R)OH] (Ar = 2,6-i-Pr2C6H3, R = H (HL1), R = Cl (HL2), and
R = Me (HL3)) were synthesized and characterized. Reaction of hydroxyindanimine with Cu(OAc)2 Æ H2O results in the formation of the
mononuclear bis(hydroxyindaniminato)copper(II) complexes Cu[ArN@CC2H3(CH3)C6H2(R)O]2 (Ar = 2,6-i-Pr2C6H3, R = H (1),
R = Cl (2), and R = Me (3)). The complex 20 was obtained from the chlorobenzene solution of the complex 2, which has the same mol-
ecule formula with the complex 2 but it is a polymorph. All copper(II) complexes were characterized by their IR and elemental analyses.
In addition, X-ray structure analyses were performed for complexes 1, 2, and 20. After being activated with methylaluminoxane (MAO),
complexes 1–3 can be used as catalysts for the vinyl polymerization of norbornene with moderate catalytic activities. Catalytic activities
and the molecular weight of polynorbornene have been investigated for various reaction conditions.
ꢀ 2007 Elsevier B.V. All rights reserved.
Keywords: Copper complex; Hydroxyindanimine ligands; Polymerization; Norbornene; Structures
1. Introduction
described in patents [3,4]. Since the past year, a few groups
have been reported some series of Cu complexes containing
ligands of N,O-chelate which can produce the vinyl-type
polynorbornene. After activation by methylaluminoxane
(MAO), both b-ketoamino Cu complexes [6] and bis(sali-
cyldiminate) Cu complexes [7] can catalyze vinyl polymer-
ization of norbornene with moderate activities. And the
b-ketoamino Cu complexes can also produce the random
co-polymer of norbornene and styrene [6b]. Recently, our
group also reported a novel Cu complex with phenoxy-
imidazole ligand which can catalyze vinyl polymerization
of norbornene with good activities [8].
It is well established that norbornene can be polymer-
ized by three different routes, affording polymeric products
that are very different in structure, properties and applica-
tions (Scheme 1) [9]. The polynorbornene (PNB) produced
by vinyl-type polymerization is a special polymer, for its
heat resistivity, high glass transition temperature, low
dielectric constant, transparency, and good solubility in
polar organic solvents. PNB has been deeply investigated
for many optical and microelectronic applications, such
In the past decade, there has been considerable activity
in the area of late transition metal olefin polymerization
catalysis [1]. However, with the exclusion of the Cu cata-
lysts systems for the atom transfer radical polymerization
(ATRP) [2], olefin polymerization catalysts based on cop-
per are considerably rare. Cu complexes with benzamidi-
nate ligands can catalyze ethylene homo-polymerization
with low catalytic activities [3]. The benzimidazolyl-ligated
Cu complexes reported by Stibrany et al. can catalyze not
only the homo-polymerization of ethylene and acrylates,
but also the co-polymerization of ethylene and acrylates
with high incorporation of acrylates [4]. Cu catalysts based
on a-diimine ligands produce very high-molecular-weight
polyethylenes with moderate activity [5], which are proba-
bly the first such olefin polymerization catalyst reported in
the academic literature, although some catalysts have been
*
Corresponding author. Fax: +86 21 65643776.
E-mail address: gxjin@fudan.edu.cn (G.-X. Jin).
0022-328X/$ - see front matter ꢀ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.06.023

G. Tang et al. / Journal of Organometallic Chemistry 692 (2007) 4106–4112
4107
Pri
ROMP
OH
R
OH
N
O
Pri
Cu(OAc)2 H2O
ethanol, reflux 3h
NH2
n
Pri
iPr
7
TiCl4
toluene,
+
1
2
6
cationic or radical
90oC, 48h
n
R
4
3
5
HL1: R=H; HL2: R=Cl; HL3: R=Me
n
n
vinyl-type
3
2
7
iPr
Pri
1
4
N
O
R
O
N
5
6
Cu
R=H(1); Cl(2); Me(3)
R
Scheme 1. Schematic representation of the three different types of
polymerization for norbornene.
iPr
Pri
Scheme 2. Synthesis of compounds HLn (n = 1,2,3) and Cu complexes
1–3.
as components for condensers, data storage and telecom-
munication waveguides [10]. Up to now, catalytic systems
based on early [11], middle [12], and late transition metal
[13] have been mainly reported for the vinyl polymerization
of norbornene.
Table 1
Crystallographic data and structure refinement details for 1, 2, and 20
Our group has designed and synthesized various nicke-
l(II) catalysts with [O, N], [N, N], [C, N] and [N, P] ligands
for vinyl polymerization for norbornene [14]. Herein, a
series of copper complexes bearing hydroxyindanimine
ligands have been synthesized, characterized, and their cat-
alytic activities have been investigated. In fact, these air-
stable, inexpensive and very ease to prepare copper com-
plexes appear good candidates for the vinyl polymerization
of norbornene.
Complex
1
2
20
Formula
Fw
C44H52CuN2O2 C44H50Cl2CuN2O2 C44H50Cl2CuN2O2
704.42
293(2)
773.30
293(2)
Monoclinic
P2(1)/c
773.30
293(2)
Triclinic
T (K)
Crystal system Monoclinic
ꢀ
Space group
Crystal size
(mm)
P2(1)/n
P1
0.25 · 0.15 · 0.10 0.20 · 0.15 · 0.10 0.25 · 0.15 · 0.10
˚
a (A)
11.716(9)
21.357(16)
16.257(12)
90
105.382(12)
90
3922(5)
4
1.193
9.557(6)
19.591(12)
11.295(7)
90
107.259(10)
90
2020(2)
2
1.272
11.88(11)
16.7(2)
21.7(2)
88.8(2)
89.05(15)
71.13(14)
4065(74)
4
1.264
0.706
0.94–27.88
16750
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
2. Results and discussion
2.1. Synthesis of hydroxyindanimine compounds and copper
complexes
3
˚
V (A )
Z
qcalc (g cmꢀ3
)
The three new hydroxyindanimine ligands HLn (n =
1,2,3) were synthesized in moderate yields by condensation
of the corresponding indanone with 2,6-diisopropylaniline
in toluene using TiCl4 as a Lewis acid catalyst (Scheme 2)
[15]. Ligands HLn (n = 1,2,3) are readily soluble in ethanol
and other common solvents such as toluene, THF, Et2O,
l (mmꢀ1
)
0.594
1.61–27.16
16992
0.711
2.08–27.19
8579
h Range (ꢁ)
Reflections
collected
Independent
reflections
Rint
8137
4454
15639
0.0698
0.0777
0.785
0.0449
0.831
1
CH2Cl2. IR, H NMR and 13C NMR spectroscopic data
Goodness-of- 0.765
fit on F2
R1 [I > 2r(I)] 0.0470
are consistent with the expected hydroxyindanimine
structure.
0.0546
0.1040
0.0589
0.1206
wR2
0.0810
When the ligands HLn (n = 1,2,3) were allowed to react
with Cu(OAc)2 Æ H2O in 2:1 molar ratio, the red-brown
Cu(II) complexes [CuLn2] (n = 1,2,3) 1–3 were obtained in
ca. 80% yields, respectively (Scheme 2) [16]. All complexes
are stable in dry air. They are very soluble in toluene, THF,
CH2Cl2, and chlorobenzene, but sparingly soluble in etha-
nol and methanol.
Crystal suitable for X-ray crystallography of complexes
1–2 were obtained by slow diffusion of ethanol into toluene
solution of the corresponding complexes. The crystallo-
graphic data and processing parameters are given in Table 1.
P
P
P
P
2
2 2
R1 = (iFoj ꢀ jFci)/ jFoj, wR2 = [ (jFoj ꢀ jFcj ) / (F2o)]1/2
.
The ORTEP diagrams of Cu(II) complexes 1 and 2 were
shown in Figs. 1 and 2, respectively. The structure analysis
shows that the molecule of complex 1 has approximate
non-crystallographic C2 symmetry, and the molecule of
complex 2 has Ci symmetry. Both complexes show the
same four-coordinate environment around the copper
atom where the two L ligands act as bidentate N,O-chela-
tors and lie in the trans conformation to create two

4108
G. Tang et al. / Journal of Organometallic Chemistry 692 (2007) 4106–4112
˚
Fig. 1. Two views of the molecular structure of complex 1 (the hydrogen atoms are omitted for clarity). Selected bond lengths (A) and angles (ꢁ): Cu(1)–
O(1) 1.884(2), Cu(1)–O(2) 1.883(2), Cu(1)–N(1) 2.005(3), Cu(1)–N(2) 2.002(3); O(1)–Cu(1)–N(1) 95.09(9), O(2)–Cu(1)–N(2) 95.16(9), O(1)–Cu(1)–O(2)
160.83(9), N(1)–Cu(1)–N(2) 156.45(8), O(1)–Cu(1)–N(2) 88.97(9), O(2)–Cu(1)–N(1) 88.58(9).
˚
Fig. 2. Two views of the molecular structure of complex 2 (the hydrogen atoms are omitted for clarity). Selected bond lengths (A) and angles (ꢁ): Cu(1)–
O(1) 1.876(2), Cu(1)–N(1) 2.014(3); O(1)–Cu(1)–N(1) 93.31(10), O(1)–Cu(1)–O(1A) 180.0, N(1)–Cu(1)–N(1A) 180.0, O(1)–Cu(1)–N(1A) 86.69(10).
six-membered chelate rings (Cu–O–C–C–C–N). However,
the geometry of copper atom in complexes 1 and 2 is differ-
ent. In complex 1, the dihedral angel of the two coordina-
tion planes (O–Cu–N) is 29.3ꢁ, suggesting a distorted
square-planar geometry. In complex 2, the copper atom
is arranged in a square-planar geometry like that observed
in the a-form of bis(N-methylsalicylaldiminato)copper
complex [17]. The bond lengths and angels are normal in
both complexes. And the presence of N-2,6-diisopropyl-
phenyl group has caused an increase in the length of the
Cu–N bond than that of the Cu–O bond. That this increase
is due to the steric effect of the N-2,6-diisopropylphenyl
group is supported by the equality of the Cu–N and Cu–
O bond lengths in bis(salicylaldiminato)copper complex
[18]. The N-2,6-diisopropylphenyl groups are roughly per-
pendicular to the remainder of the ligand L, making an
angle of 86.1ꢁ or 85.9ꢁ with the two hydroxyindanimine-
residues in complex 1 and an angle of 83.2ꢁ in complex 2
[19].
complex 2 and complex 20. The complex 20 was obtained
from the slow diffusion of ethanol into chlorobenzene solu-
tion of the complex 2 (Scheme 3). However, the complex 2
was not obtained from the toluene solution of the complex
20.
The crystallographic data and processing parameters of
the complex 20 are summarized in Table 1. The ORTEP
diagrams of Cu(II) complexes 20 was shown in Fig. 3.
For complex 20, there are two independent molecules in a
crystal cell. The geometry of each molecule is similar to
that of the complex 1. The two copper atoms are arranged
in a distorted square-planar geometry with a dihedral angel
31.6ꢁ (Cu(1)) and 31.9ꢁ (Cu(2)) of the two coordination
planes (O–Cu–N), respectively. The N-2,6-diisopropylphe-
nyl groups are also roughly perpendicular to the remainder
of the ligand L, making an angle of 89.8ꢁ or 89.3ꢁ (Cu(1))
and 88.9ꢁ or 89.2ꢁ (Cu(2)) with the two hydroxyindani-
mine-residues, respectively. Those angles are about 3ꢁ
Polymorphism is a feature of a number of coordination
compounds which has long been recognized [20]. Like
bis(N-methylsalicylaldiminato)copper complex, which has
three different isomers—a-, b-, and c-form [17,21], there
are two different isomers in the copper complex [CuL22]:
chlorobenzene 2'
2
toluene
Scheme 3. Two isomers of complex [CuL22].

G. Tang et al. / Journal of Organometallic Chemistry 692 (2007) 4106–4112
4109
0
˚
Fig. 3. Two views of the molecular structure of complex 2 (the hydrogen atoms are omitted for clarity). Selected bond lengths (A) and angles (ꢁ): Cu(1)–
O(1) 1.864(16), Cu(1)–O(2) 1.886(16), Cu(1)–N(1) 2.017(18), Cu(1)–N(2) 2.02(2); O(1)–Cu(1)–N(1) 94.5(3), O(2)–Cu(1)–N(2) 95.6(2), O(1)–Cu(1)–O(2)
158.38(19), N(1)–Cu(1)–N(2) 155.4(3), O(1)–Cu(1)–N(2) 88.8(2), O(2)–Cu(1)–N(1) 90.3(4).
Table 2
greater than that in complex 1. The distance of Cl(1) atom
and Cl(4) atom of the another molecule is 3.541 A, and that
Norbornene Polymerization for the 1/MAO catalytic systema
˚
Run
Al/Cu
T (ꢁC)
Yield (mg)
Activityb
Mvc
of Cl(2) atom and Cl(3) atom of the another molecule is
˚
3.466 A. That distances indicated the presence of the weak
1
2
3
4
5
6
7
8
a
300
550
750
1050
1500
750
30
30
30
30
30
16
45
60
10
78
95
84
78
77
74
67
1.0
7.8
9.5
8.4
7.8
7.7
7.4
6.7
–
1.22
1.36
1.20
1.04
0.50d
1.38
1.31
Clꢁ ꢁ ꢁCl interaction between two chlorine atoms. Similarly,
there are the presence of the weak Clꢁ ꢁ ꢁH–C interaction
between the chlorine atom and the methyl group of the iso-
˚
propyl group, supported by the distance 3.466 A between
Cl(2) atom and C(62) of the another molecule and the dis-
750
750
˚
tance 3.479 A between Cl(4) atom and C(18) of the another
molecule.
Polymerization conditions: Cu = 1.0 lmol; NB = 0.952 g; time = 1 h;
Vtotal = 10.0 mL; solvent: chlorobenzene.
b
104 g PNB molꢀ1 Cu hꢀ1
.
3. Norbornene polymerization
c
106 g molꢀ1
.
d
Not completely dissolved.
The norbornene polymerization results using the copper
complexes 1–3/MAO as catalytic systems are summarized
in Tables 2 and 3.
Chlorobenzene was chosen as the reaction medium for
norbornene polymerization because it can improve the cat-
alytic performances due to its polarity [9].
Table 3
Norbornene polymerization with different complexesa
Run
1
Cat
Yield (mg)
Activityb
Mvc
1
95
47
110
–
9.5
4.7
11.0
–
1.36
1.58
1.76
–
No catalytic activity was observed for complex 1–3 in
the absence of MAO. Therefore, the co-catalyst MAO is
essential for the norbornene polymerization catalyzed by
complex 1–3. After activation with MAO, Cu (II) com-
plexes 1–3 can catalyze norbornene (NB) polymerization
(Table 1, runs 1–8; Table 2, runs 1–3).
Preliminary experiments on norbornene polymerization
were performed in the presence of complex 1 as catalytic
precursor. Variation of the Al/Cu ratio shows a significant
effect on the catalytic activities and molecular weight
(Table 1, runs 1–5). The catalytic activities of 1 increase
first and then slowly decrease with the increase of the
Al/Cu ratio under the experimental conditions. The highest
activity of 9.5 · 104 g PNB molꢀ1 Cu hꢀ1 is observed at Al/
Cu ratio of 750/1 (Table 1, run 3). All polymers display
high molecular weights (Mv up to 106 g molꢀ1). The effect
of Al/Cu ratio on molecular weight of polymers is similar
to that effect on catalytic activities. Mv increases first and
then decreases with the increase of Al/Cu ratio. The highest
d
2
2
3
4
a
3
20
Polymerization conditions: Cu = 1.0 lmol; NB = 0.952 g; Al/
Cu = 750; T = 30 ꢁC; time = 1 h; Vtotal = 10 mL; solvent, chlorobenzene.
b
104 g PNB molꢀ1 Cu hꢀ1
.
c
106 g molꢀ1
.
d
Freshly dissolved in chlorobenzene.
Mv of 1.36 · 106 g molꢀ1 is also observed at Al/Cu ratio of
750/1 (Table 1, run 3). The reaction temperature also
affects considerably the catalytic activities and molecular
weight (Table 1, runs 3, 6–8). With an increase of reaction
temperature, the catalytic activities and Mv’s of polymers
first increase and then decrease. The maximum value of
activities is obtained at 30 ꢁC (Table 1, run 3), while that
of Mv of polymer (up to 1.38 · 106 g molꢀ1) is observed
at 45 ꢁC (Table 1, run 7).

4110
G. Tang et al. / Journal of Organometallic Chemistry 692 (2007) 4106–4112
The structures of the copper complexes also affect consid-
ized, which were air-stable, inexpensive, and very easy to
prepare. After activation with MAO, the resulting cop-
per(II) complexes show moderate catalytic activities for
the vinyl polymerization of norbornene. The investigations
on the mechanism of polymerization are under way.
erably the catalytic activities and molecular weights (Table 2,
runs 1–4). When 1 was replaced by 2 containing a chlorine
atom, the activity is 4.7 · 104 g PNB molꢀ1 Cu hꢀ1, which
is half of that of complex 1 under the same experimental con-
ditions (Table 2, run 2). When complex 3 bearing a methyl
group was used as catalyst, the highest activity up to
11.0 · 104 g PNB molꢀ1 Cu hꢀ1 is obtained in all experi-
ment on norbornene polymerization (Table 2, run 3). The
difference of activities resulting from the difference of molec-
ular structure may be due to the different electronic effect of
R group of ligands HLn (n = 1,2,3). The Mv of polynor-
bornene obtained varies from 1.36 · 106 g molꢀ1 to
1.76 · 106 g molꢀ1. To our surprised, the complex 20 can
not catalyze norbornene polymerization to produce poly-
norbornene under our experimental conditions (Table 2,
run 4). The reason is indistinct.
5. Experimental
5.1. General procedures
All air-sensitive experiments were carried out under
nitrogen using standard Schenk techniques. Chlorobenzene
was dried over CaH2 and distilled under nitrogen prior to
use. Norbornene was purchased from ACROS and purified
by distillation over sodium. Methylaluminoxane (MAO)
was purchased from Aldrich as 10% weight of a toluene
solution and used without further purification. 2,6-Diiso-
propylaniline (90%) was purchased from Lancaster. Other
chemicals were of analytical grade and were used as
received. FTIR spectra were recorded on a Niclolet FTIR
spectrometer. Element analyses were performed on an Ele-
The microstructure of the obtained polynorbornene is
characterized by FTIR spectra and 1H NMR and 13C
NMR spectra. Those spectra are typical of a vinyl-type
structure. In FTIR spectra, there are no absorptions at
1680–1620 cmꢀ1
,
especially about 960 cmꢀ1 and
mentar vario EL III Analyzer. H and 13C NMR spectra
1
735 cmꢀ1, assigned to the trans and cis form of double
bonds, respectively, which are characteristic of the ROMP
structure of polynorbornenes [22]. On the contrary, these
absorption peaks at about 942 cmꢀ1, which can be assigned
to the ring system of bicycle [2.2.1] heptane as Kenndy
noted, are observed [23].
were carried out on a Bruker AC 500 spectrometer instru-
ment at room temperature in CDCl3 solution for ligands,
and o-dichlorobenzene-d4 solution for polymers using
TMS as internal standard. The intrinsic viscosity [g] was
measured in chlorobenzene at 25 ꢁC using an Ubbelohde
viscometer. Viscosity average molecular weight (Mv) values
of polymer were calculated by the following equation:
[g] = 5.97 · 10ꢀ4 Mv0.56 [27]. Differential scanning calori-
metric (DSC) measurements were performed on a Per-
kin–Elmer Pyris 1 DSC. The wide-angle X-ray diffraction
(WAXD) diagram of the polymer powders was obtained
using a Bruker D4 Endeavor X-ray diffractometer. Scan-
ning was performed with 2h ranging from 5ꢁ to 60ꢁ.
7-Hydroxy-3-methylindan-1-one, 7-hydroxy-3,4-dimethy-
lindan-1-one and 4-chloro-7-hydroxy-3-methylindan-1-
one were prepared according to literature procedures [28].
1H NMR and 13C NMR spectra confirmed the above
1
conclusions. H NMR spectra show signals in the 0.9–3.0
ppm range, where no resonances are displayed at about d
1
5.1 and 5.3 ppm in the H NMR spectrum of the polynor-
bornene, assigned to the cis and trans form of double
bonds [24], which generally indicates the presence of the
ring-opening metathesis polymerization (ROMP) struc-
ture. The 13C NMR spectrum shows the main four groups
of resonances: d (51.3, 50.4, 49.2, 47.0, 46.3, 45.9), (41.0,
40.3, 39.4, 38.3), (37.8, 36.8, 35.7, 34.8), (32.0, 30.3, 28.9,
28.4) ppm, attributed to the carbons 2 and 3, carbons 1
and 4, carbon 7, carbons 5 and 6, respectively (Scheme 1)
[25]. The 13C NMR spectrum is similar to that reported
by Patil et al. [26]. These data indicate that the polynor-
bornene obtained with the aforementioned catalysts was
a vinyl-type (2,3-linked) product.
All the polynorbornenes synthesized here are easily sol-
uble in cyclohexane, chlorbenzene and o-dichlorobenzene,
which indicated the low stereoregularity. Indeed, analysis
by wide-angle X-ray diffractometry shows no indication
of crystallinity. Our attempts to determine the glass transi-
tion temperature (Tg) of polynorbornenes failed, DSC
studies not giving an endothermic signal upon heating to
450 ꢁC [14].
5.2. Synthesis of 7-hydroxy-3-methylindan-1-(N-2,
6-diisopropylphenylimine) (HL1)
To a stirred solution of 2,6-diisopropylaniline (8.6 mL,
45.4 mmol) in toluene (40 mL) was added TiCl4 (1.3 mL,
11.4 mmol) in toluene (30 mL) at room temperature during
30 min. The resulting mixture was stirred at 90 ꢁC for
30 min followed by the addition of 7-hydroxy-3-methylin-
dan-1-one (1.84 g, 11.4 mmol). The mixture was stirred
for 48 h at 90 ꢁC, poured into saturated Na2CO3 solution,
and extracted with ethyl ether. The organic phase was dried
over anhydrous Mg2SO4. Evaporating the solvent, purifi-
cation by column chromatography on silica gel using hex-
ane/ethyl acetate (200/1) as eluent gave compound HL1
1
4. Conclusion
(1.58 g, 4.9 mmol) as an orange-red oil in 43% yield. H
NMR (500 MHz, CDCl3): d 1.13–1.30 (m, 15H), 2.05
(dd, 1H), 2.67 (dd, 1H), 2.89 (m, 2H), 3.41 (m, 1H),
6.84–7.40 (m, 6H), 11.78 (br, 1H); 13C NMR (125 MHz,
In this work, a series of copper(II) complexes containing
hydroxyindanimine ligand were synthesized and character-

G. Tang et al. / Journal of Organometallic Chemistry 692 (2007) 4106–4112
4111
CDCl3): d 22.8, 23.2, 24.2, 28.7, 35.9, 39.7, 113.9, 115.4,
118.8, 122.8, 123.1, 123.6, 125.1, 132.5, 134.6, 137.6,
145.7, 156.2, 158.3, 178.8; IR (KBr): m 3062 (w), 2962 (s),
2927 (m), 2869 (m), 1640 (s), 1596 (m), 1471 (m), 1437
(w), 1382 (w), 1362 (m), 1318 (w), 1290 (m), 1263 (m),
1216 (m), 1184 (m), 1158 (w), 1106 (w), 1051 (w), 955
(w), 879 (w), 835 (w), 796 (m), 741 (m), 690 cmꢀ1 (w); Anal.
Calc. for C22H27NO: C, 82.20; H, 8.46; N, 4.36. Found: C,
81.92; H, 8.41; N 4.40%.
(20 mL) at the refluxing temperature for 3 h. After cooling,
the solid was filtered and recrystallized from a toluene/eth-
anol solution at room temperature to give complex 1
(0.321 g, 0.456 mmol) as red-brown crystals in 80% yield.
The other copper(II) complexes 2–3 were prepared by the
same procedure.
Complex 1: IR (KBr, cmꢀ1): m 3056 (w), 2958 (s), 2922
(m), 2865 (m), 1605 (vs), 1557(s), 1468 (s), 1437 (w), 1411
(w), 1354 (m), 1288 (w), 1236 (m), 1181 (w), 1153 (w),
1049 (w), 967 (w), 795 (m), 763 (w), 744 (w); Anal. Calc.
for C44H52CuN2O2: C, 75.07; H, 7.45; N, 3.98. Found: C,
74.75; H, 7.28; N, 3.91%.
5.3. Synthesis of 4-chloro-7-hydroxy-3-methylindan-1-
(N-2,6-diisopropylphenylimine) (HL2)
Complex 2: IR (KBr, cmꢀ1): m 3060 (w), 2958 (s), 2924
(m), 2866 (m), 1612 (vs), 1550 (s), 1466 (s), 1398 (w),
1356 (s), 1322 (w), 1235 (s), 1172 (m), 1116 (w), 1062 (w),
935 (w), 869 (w), 823 (m), 797 (m), 770 (m), 730 (m); Anal.
Calc. for C44H50Cl2CuN2O2: C, 68.46; H, 6.53; N, 3.63.
Found: C, 68.32; H, 6.49; N, 3.58%.
Analogous synthesis to HL1, except that 4-chloro-7-
hydroxy-3-methylindan-1-one instead of 7-hydroxy-3-
methylindan-1-one was used. Purification by column
chromatography on silica gel using hexane/ethyl acetate
(200/1) as eluent gave compound HL2 as a red-yellow solid
in 40% yield. 1H NMR (500 MHz, CDCl3): d 1.12–1.35 (m,
15H), 2.14 (dd, 1H), 2.69 (dd, 1H), 2.80 (m, 1H), 2.91 (m,
1H), 3.50 (m, 1H), 6.82 (d, 1H), 7.14–7.31 (m, 4H), 11.76
(br, 1H); 13C NMR (125 MHz, CDCl3): d 20.7, 22.9,
23.1, 23.8, 23.9, 28.5, 35.7, 39.4, 115.8, 120.9, 123.5,
125.0, 134.3, 137.4, 144.9, 151.9, 156.8, 178.3; IR (KBr):
m 3062 (w), 2962 (s), 2927 (m), 2869 (m), 1640 (s), 1596
(m), 1471 (m), 1437 (w), 1382 (w), 1362 (m), 1318 (w),
1290 (m), 1263 (m), 1216 (m), 1184 (m), 1158 (w), 1106
(w), 1051 (w), 955 (w), 879 (w), 835 (w), 796 (m), 741
(m), 690 cmꢀ1 (w); Anal. Calc. for C22H26ClNO: C,
74.24; H, 7.36; N, 3.94. Found: C, 74.11; H, 7.28; N 3.87%.
Complex 3: IR (KBr, cmꢀ1): m 3053 (w), 2956 (s), 2922
(m), 2866 (m), 1609 (vs), 1553 (s), 1481 (s), 1398 (w),
1350 (m), 1235 (m), 1184 (w), 1160 (w), 1100 (w), 1073
(w), 906 (w), 867 (w), 824 (m), 803 (m), 773(m); Anal. Calc.
for C46H56CuN2O2: C, 75.48; H, 7.72; N, 3.83. Found: C,
75.32; H, 7.68; N, 3.81%.
5.6. Synthesis of copper(II) complex 20
The complex 2 was added to the stirred chlorobenzene
solvent. The stirring procedure lasted five days. And com-
plex 20 was obtained by the slow diffusion of ethanol into
the chlorobenzene solution at room temperature.
5.4. Synthesis of 7-hydroxy-3,4-dimethylindan-1-(N-2,
6-diisopropylphenylimine) (HL3)
5.7. X-ray crystallography
Analogous synthesis to HL1, except that 7-hydroxy-3,4-
dimethylindan-1-one instead of 7-hydroxy-3-methylindan-
1-one was used. Purification by column chromatography
on silica gel using hexane/ethyl acetate (200/1) as eluent
gave compound HL3 as a red-yellow solid in 40% yield.
1H NMR (500 MHz, CDCl3): d 1.11–1.28 (m, 15H), 2.08
(dd, 1H), 2.30 (s, 3H), 2.67 (dd, 1H), 2.84 (m, 1H), 2.96
(m, 1H), 3.43 (m, 1H), 6.77 (d, 1H), 7.14–7.18 (m, 4H),
11.78 (br, 1H); 13C NMR (125 MHz, CDCl3): d 17.4,
21.4, 22.6, 22.9, 23.1, 23.7, 23.9, 28.0, 28.4, 35.1, 39.7,
113.8, 118.6, 122.9, 123.3, 124.7, 132.5, 137.4, 145.4,
153.5, 156.1, 178.9; IR (KBr): m 3060 (w), 2961 (s), 2868
(m), 1634 (s), 1594(m), 1461 (m), 1381 (w), 1361 (w),
1319 (w), 1287 (m), 1253 (m), 1221 (m), 1184 (w), 1107
(w), 1050 (w), 933 (w), 900 (w), 823 (m), 764 (w), 733
(m), 691 cmꢀ1 (w); Anal. Calc. for C23H29NO: C, 82.34;
H, 8.71; N, 4.18. Found: C, 82.19; H, 8.78; N, 4.22%.
Diffraction data of complexes 1, 2, and 20 were collected
on a Bruker Smart APEX CCD diffractometer with graph-
˚
ite-monochromated Mo Ka radiation (k = 0.71073 A). All
the data were collected at room temperature and the struc-
tures were solved by direct methods and subsequently
refined on F2 by using full-matrix least-squares techniques
(SHELXL) [29], absorption corrections were applied to the
data. The non-hydrogen atoms were refined anisotropi-
cally, and hydrogen atoms were located at calculated
positions.
5.8. Norbornene polymerization
In a typical procedure (Table 1, run 3), 1.0 lmol of cop-
per(II) complex 1 in 1.0 mL of chlorobenzene, 0.952 g of
norbornene in 2.0 mL of chlorobenzene and another fresh
chlorobenzene were added into a polymerization bottle
with a strong stirred under a nitrogen atmosphere. After
the mixture was kept at 30 ꢁC for 5 min, 0.5 mL of MAO
was charged into the polymerization system by means of
a syringe and the reaction was initiated. Ten minutes later,
acidic methanol (Vethanol:Vconcd.HCl = 20:1) was added to
terminate the reaction. The polymer was isolated by
5.5. Synthesis of copper(II) complexes (1–3)
7-Hydroxy-3-methylindan-1-(N-2,6-diisopropylphenyli-
mine) (0.356 g, 1.14 mmol) was allowed to react with
Cu(OAc)2 Æ H2O (0.114 g, 0.57 mmol) in anhydrous ethanol

4112
G. Tang et al. / Journal of Organometallic Chemistry 692 (2007) 4106–4112
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479;
filtration, washed with methanol and dried at 80 ꢁC for
48 h under vacuum. For all polymerization procedures,
the total reaction volume was 10.0 mL, which can be
achieved by varying the amount of chlorobenzene when
necessary. IR (KBr, cmꢀ1): m 2947 (s), 2869 (s), 1476 (m),
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CCDC 644803, 644804 and 644805 contain the supple-
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Acknowledgements
Financial support by the National Science Foundation
of China for Distinguished Young Scholars (20421303,
20531020), by the National Basic Research Program of
China (2005CB623800) and by Shanghai Science and Tech-
nology Committee (05JC14003, 05DZ22313) is gratefully
acknowledged.
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