Synthesis of zirconocenes bearing benz[f]indenyl ligand and their use as a catalyst in ethylene polymerization

Article abstract of DOI:10.1016/j.jorganchem.2005.02.008

Benz[f]indenyl zirconium complexes have been successfully synthesized and characterized. Their catalytic activities were evaluated for the polymerization of ethylene. The complexes combined with MAO can be highly active single site catalysts, which displa

Full text of DOI:10.1016/j.jorganchem.2005.02.008

Journal of Organometallic Chemistry 690 (2005) 1822–1828
www.elsevier.com/locate/jorganchem
Synthesis of zirconocenes bearing benz[f]indenyl ligand and their
use as a catalyst in ethylene polymerization
a
Do Han Kim , Jung A Lee , Bun Yeoul Lee , Young Keun Chung
a
b
a,
*
a
Department of Chemistry, Seoul National University, Seoul 151-747 N60, Korea
b
Department of Molecular Science and Technology, Ajou University, Suwon 442-749, Korea
Received 5 November 2004; accepted 8 February 2005
Available online 16 March 2005
Abstract
Benz[f]indenyl zirconium complexes have been successfully synthesized and characterized. Their catalytic activities were evalu-
ated for the polymerization of ethylene. The complexes combined with MAO can be highly active single site catalysts, which display
activities comparable with that of the Cp2ZrCl2/MAO system and provide very high molecular weight polyethylenes. The melting
point of the polymers indicates the formation of linear polyethylene.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Benz[f]indenyl; Zirconium; Cyclopentadienyl; Ethene; Polymerization
1. Introduction
of metallocenes allows rational catalyst design to eluci-
date a qualitative relationship between catalyst structure
and the resulting polymer microstructure [4].
The discovery of the combination of group 4 metal-
locenes and methylaluminoxane (MAO) as catalysts in
the olefin polymerization opens the gateway to a new
world of polymers [1]. Thus, there has been active re-
search aimed at discovering analogues or alternatives
for the cyclopentadienyl (Cp) ring since changes to the
ligand skeleton provides access to more unusual mate-
rials, which are unachievable using conventional
Ziegler–Natta catalysts (For reviews on metallocene
olefin polymerization, see: [2]). For example, indenyl,
fluorenyl, cyclohexadienyl, boratabenzene anion, bor-
ole, azaborolinyl, cyclooctatetraenyl dianion, trimethyl-
ene dianion, and tripyrazolyl anion have been used
instead of Cp [3]. Nowadays, the well-defined nature
Benz[f]indenyls, isomer to fluorenyls, have not been
used as alternatives or substitutes for Cp until we re-
cently reported [5] the first synthesis of zirconium com-
plexes of benz[f]indenyl ligands. There had been some
efforts to synthesize metallocenes bearing benz[f]inde-
nyls [6]. However, their attempts were not successful
presumably due to the low stability of benz[f]indenyl an-
ions. In order to overcome this problem, we introduced
some substituents to the benz[f]indenyl skeleton. Finally,
several zirconium compounds of benz[f]indenyls were
synthesized and one of them was characterized by X-
ray crystallography. Thus, we expect that the use of
benz[f]indenyl ligands in the synthesis of metallocenes
will be quite common in the near future. Herein, we re-
port the synthesis of Zr complexes of benz[f]indenyls
and their catalytic activity in ethylene polymerization
in detail.
*
Corresponding author. Tel.: +8228806662; fax: +8228890310.
E-mail addresses: ykchung@snu.ac.kr, ykchung@plaza.snu.ac.kr
(Y.K. Chung).
0022-328X/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.02.008

D.H. Kim et al. / Journal of Organometallic Chemistry 690 (2005) 1822–1828
1823
2. Results and discussion
was extracted with dichloromethane and filtered off to
remove lithium chloride. After removal of the solvent,
a crude product was obtained. None of the zirconium
compounds were soluble in diethyl ether and hexane
but all soluble in dichloromethane. Compounds 1–3
were soluble in toluene but 4–6 were almost insoluble
in toluene. Thus, the solubility was highly dependent
upon the presence of the substituents. After recrystalli-
zation in toluene/Et2O, reddish crystalline solids were
obtained for 1, 2, and 3. Yellowish powders were ob-
tained for 4, 5, and 6.
2.1. Synthesis
Zirconium complexes synthesized in this study were
drawn in Chart 1. Schemes 1 and 2 show the synthetic
pathway to benz[f]indenyl zirconium compounds 1 and
4, respectively. For the synthesis of 2 and 3, the same
procedure as the synthesis of 1 was applied and for 5
and 6 the same procedure as the synthesis of 4 was ap-
plied. In order to know the effect of a substituent of
the benz[f]indene on the catalytic activity and the molec-
ular weight of polymers, two kinds of benz[f]indene
compounds, i.e., both with and without substituents,
were used in the synthesis of zirconium complexes.
Substituted benz[f]indenes [5] and unsubstituted
benz[f]indene [7] were prepared by the procedure of
the literature. The benz[f]indenes having substituents
were not soluble in diethyl ether but soluble in THF at
ꢀ78 ꢁC. Lithiation was conducted in THF solution.
However, benz[f]indene without substituents was solu-
ble in diethyl ether and THF at ꢀ78 ꢁC. Thus, lithiation
could be carried out in either solution. After evapora-
tion, gummy solids were obtained. The gummy solids
were transferred into a dry box and dissolved in toluene.
In order to synthesize zirconium metallocene com-
pounds, three kinds of zirconium chloride compounds,
(Ind)ZrCl3 (Ind = indenyl), Cp*ZrCl3, and CpZrCl3,
were used. They were not very soluble in toluene, but
slowly dissolved in toluene as the reaction proceeded.
For example, as the reaction of gummy solids with
(Ind)ZrCl3 proceeded, (Ind)ZrCl3 was slowly dissolved
in toluene. After evaporation of toluene, the residue
2.2. X-ray diffraction study
Single crystals of 1 and 2 were obtained by recrystal-
lization from a dichloromethane/toluene mixture at
ꢀ20 ꢁC. The crystal structure of 2 was previously com-
municated [5]. Figs. 1 and 2 give ORTEP views of the
structures of 1 and 2 together with the atom labeling.
Crystal data, details of the data collection, and refine-
ment parameters are listed in Table 1 and selected bond
distances and angles are given in Table 2. The geometry
around Zr, as defined by the centroids of the cyclopen-
tadienyl, benz[f]indenyl and Cl atoms, is roughly tetra-
hedral. Although the substitution of the methyl group
on the cyclopentadienyl causes no apparent distortion
of the structure, all the Zr–C bond lengths for 2 are
longer than those found in 1 presumably due to the ste-
ric bulkiness of Cp*. For a bent metallocene, geometric
parameters (a, b, and c) were proposed [8]. The angle be-
tween the ring planes (a) was 52.8ꢁ and 48.6ꢁ for 1 and 2,
respectively. The ring centroid–metal–ring centroid (c)
was 130.5ꢁ and 134.5ꢁ for 1 and 2, respectively. The
Ph
Ph
Ph
Cl
Cl
Cl
Cl
Cl
Zr
Zr
Zr
Cl
1
2
3
Cl
Cl
Cl
Cl
Cl
Cl
Zr
Zr
Zr
4
5
6
Chart 1. Structures of synthesized zirconium complexes.

1824
D.H. Kim et al. / Journal of Organometallic Chemistry 690 (2005) 1822–1828
cat. Co2(CO)8
O
O
CO 30atm
Ph
H
H
HCl
O
O
Ph
Ph
1b
CH2Cl2
MeOH
1a
Pd/C
THF
OH
O
MgSO4
toluene
LAH
THF
Ph
1d
Ph
Ph
1c
1) n-BuLi
2) CpZrCl3
Ph
Cl
Zr
Cl
1
Scheme 1. Syntheses of substituted benz[f]indenyl zirconium complex 1.
O
OH
LAH
THF
MgSO4
-H2O
1) n-BuLi
Cl
Cl
Zr
2) CpZrCl3
4
Scheme 2. Syntheses of benz[f]indenyl zirconium complex 4.
Fig. 1. Drawing of compound 1. Atoms are represented by anisotropic
displacement ellipsoids at the 30% probability level.
angle b between the normals from the metal to the ring
planes, is another useful parameter, because its differ-
ence from c reflects the amount of slippage of the metal
from an ideal g5 coordination to each ring [9]. The b va-
lue was 127.2ꢁ and 131.4ꢁ for 1 and 2, respectively. Thus,
the angle is greater than the angle b. Interestingly, the
difference between b and c for 1 and 2 was almost the
same.
The benz[f]indenyl groups are displaced from sym-
metric g5-coordination toward g3-coordination: for
example, the Zr is significantly closer to carbons C(1),
C(2), and C(13) than carbons C(3) and C(12). We
expected that this modified g3–g2 coordination geometry
creates a more electrophilic metal center [8].
2.3. Polymerization of ethylene
The dichloride complexes 1–6 are active to ethylene
polymerization when activated with MAO. The activi-
ties of unsubstituted benz[f]indenyl zirconium complexes
(4–6) were greater than those of substituted benz[f]inde-
nyl zirconium complexes (1–3). The highest activity

D.H. Kim et al. / Journal of Organometallic Chemistry 690 (2005) 1822–1828
1825
Table 2
Selected bond lengths (A) and angles (ꢁ) for 1 and 2
˚
1
2
Zr–Cl1
Zr–Cl2
2.4243(18)
2.4390(16)
2.556(5)
2.487(6)
2.614(5)
2.602(5)
2.524(6)
2.488(6)
2.473(7)
2.508(8)
2.497(8)
2.471(8)
96.40(7)
2.194
2.4591(11)
2.4218(15)
2.576(5)
2.572(4)
2.643(5)
2.592(4)
2.465(4)
2.510(6)
2.514(6)
2.515(6)
2.532(6)
2.511(6)
95.25(5)
2.232
Zr–C1
Zr–C2
Zr–C3
Zr–C12
Zr–C13
Zr–C22
Zr–C23
Zr–C24
Zr–C25
Zr–C26
Cl1–Zr–Cl2
Zr–Cp(c)a
Zr–benzind(c)b
Cpbenzind(c)–Zr–Cp(c)
a
2.250
130.58
2.267
134.52
Fig. 2. Drawing of compound 2. Atoms are represented by anisotropic
displacement ellipsoids at the 30% probability level.
Centroid of cyclopentadienyl group.
b
Centroid of benz[f]indenyl group.
Table 1
Crystal data and structure refinement for 1 and 2a
Table 3
Ethylene polymerizations by benz[f]indenyl zirconium complexesa
Compound
1
2
Entry Compound Activityb Mw (·105) Mw/Mn Melting
point (ꢁC)
Formula
Mw
C26H22ZrCl2
496.59
C31H32ZrCl2
566.72
Unit cell dimensions
˚
1
2
3
4
5
6
7
Cp2ZrCl2
24
24
22
3.8
1.9
1.92
1.88
2.23
1.72
2.07
2.64
2.43
134.3
134.6
134.2
133.7
134.4
136.2
135.4
a (A)
˚
8.5676(3)
10.2271(4)
13.1520(5)
98.134(2)
91.938(2)
108.011(2)
1081.22(7)
Triclinic
P ꢀ 1
9.3370(10)
18.0230(10)
16.1490(10)
90
1
2
3
4
5
6
b (A)
˚
c (A)
7.5
7.9
10.3
6.3
a (ꢁ)
b (ꢁ)
c (ꢁ)
30
39
26
100.296(2)
90
2.8
3.4
3
˚
V A
2673.8(4)
Monoclinic
P21/n
a
Polymerization conditions: 30 mL of toluene, 0.29 lmol of com-
Crystal system
Space group
plex, [Al]/[Zr] = 5000, 60 ꢁC, 5 min.
Activity in 106 gmol Zr Æ h.
b
Z
2
4
0.629
l/mmꢀ1
No. of data collected
0.766
7296
7826
4445
over, the PEs produced by this study are highly linear
with Tm = 133–136 ꢁC. The above results show that
the activity, molecular weight, and PDI value of the
(benz[f]indenyl)zirconium complexes are highly depen-
dent upon the steric effect of an ancillary ligand. For
1–3, as the steric effect of the ancillary ligand increases
(Indenyl > Cp* > Cp), the activity decreases but the
molecular weight increases. However, for 4–6, there is
an optimum steric crowdedness for the maximum activ-
ity: the activity decreases in the order of 5 > 4 > 6 and
the molecular weight decreases in the order 4 > 6 > 5
(Table 3).
No. of unique data
No. of variables
4971
266
315
0.0409
0.0679
R
Rw
a
0.0619
0.1888
Data collected at 293(2) K with Mo Ka radiation (k(Ka) =
2
0.7107A), R(F) = RiFo|ꢀ|Fci/R|Fo| with Fo > 2.0r(I), Rw ¼ ½R½wðF 2o ꢀ F c2Þ ꢁ=
2 2 1=2
R½wðF oÞ ꢁ ꢁ with Fo > 2.0r(I).
(39 · 106 g/mol of Zr h) was observed for 5 and 3 shows
the lowest activity (7.9 · 106 g/mol of Zr h) with the
highest molecular weight, 10.3 · 105. Interestingly, the
activity of 6 and the molecular weight of polyethylene
produced by 6 are comparable to that of Cp2 ZrCl2
but 4 and 5 have much higher activities. Molecular
weights of the obtained polyethylenes are fairly high in
the cases of 2 and 3. In many cases, high molecular
weight polyethylenes are produced by the catalysts with
bulky substitutents in the ligand sphere with substantial
loss of activity [10]. The molecular weight distributions
are narrow (Mw/Mn, 1.7–2.6) indicating a single active
species is present in the polymerization solution. More-
3. Conclusions
A new series of benz[f]indenyl zirconium complexes
were successfully prepared and characterized. They
were highly active catalysts in the presence of MAO
for polymerization of ethylene. They display activities
comparable with that of Cp2ZrCl2/MAO systems. We

1826
D.H. Kim et al. / Journal of Organometallic Chemistry 690 (2005) 1822–1828
expect that the benz[f]indenyl zirconium catalysts are
an important addition to the list of group 4 metallo-
cene catalysts. Efforts to synthesize catalysts with sub-
stitution in the special positions of benz[f]indenyl
framework and their influence on the polymer proper-
ties are in progress.
pounds. The ethyl acetate extract was dried over
anhydrous MgSO4, filtered, and chromatographed on
a silica gel column eluting with hexane and ethyl ace-
1
tate (v/v, 10:1). Yield: 90%; H NMR (CDCl3): d8.07
(d, J = 6.8 Hz, 1H), 7.98 (s, 1H), 7.92 (d, J = 7.7 Hz,
1H), 7.88 (d, J = 7.0 Hz, 2H), 7.58 (t, J = 7.0 Hz,
1H), 7.49 (t, J = 7.1 Hz, 1H), 7.42 (t, J = 7.5 Hz,
2H), 7.34 (t, J = 7.2 Hz, 1H), 2.92 (s, 3H), 2.58 (s,
3H); 13C NMR (CDCl3): d197.2, 141.7, 141.6, 139.1,
136.1, 135.9, 135.8, 134.7, 132.2, 128.7, 128.6, 128.5,
127.5, 126.9, 126.7, 126.3, 125.5, 13.8, 12.0; IR
4. Experimental
4.1. General remarks
m(C@O) 1694 cmꢀ1
;
284.1201, obsd. 284.1201.
HRMS for C21H16O: Calc.
Toluene used for polymerization reaction was pur-
chased from Aldrich (anhydrous grade) and purified fur-
ther over Na/K alloy. Ethylene was purchased from
Conley Gas (99.9%) and purified by contacting with
molecular sieves and copper overnight under the pres-
sure of 150 psig. Methylaluminoxane (MAO) was pur-
chased as a solution in toluene from Akzo (7.6 wt% of
Al, MMAO type 4). Gel permeation chromatograms
(GPC) were obtained at 140 ꢁC in trichlorobenzene
using Waters Model 150-C+ GPC and the data were
analyzed using a polystyrene analyzing curve.
4.4. 4,9-Dimethyl-2-phenylbenz[f]indan-1-one (1c)
To a 50 mL schlenk flask filled with nitrogen were
added a solution of 1b (0.30 g,1.06 mmol) in 25 mL of
THF and Pd/C (0.30 g, Pd 10%, dry wt. basis Water
ꢂ50%). The solution was flushed with a balloon of H2
gas. When the yellow color of the solution was disap-
peared, the reaction was completed. Pd/C was recovered
by filtration and reused for other reaction. Filtrate was
concentrated and chromatographed on a silica gel col-
umn eluting with hexane and ethyl acetate (v/v, 9:1).
Yield: 93%; 1H NMR (CDCl3): d8.27 (d, J = 8.4 Hz,
1H), 8.09 (d, J = 8.4 Hz, 1H), 7.66 (t, J = 8.4 Hz, 1H),
7.56 (t, J = 8.4 Hz, 1H), 7.32–7.20 (m, 5H), 3.95 (dd,
J = 4.8, 9.1 Hz, 1H), 3.73 (dd, J = 9.1, 17 Hz, 1H),
3.28 (dd, J = 4.7, 17 Hz, 1H), 3.07 (s, 3H), 2.65 (s,
3H); 13C NMR (CDCl3): d 208.2, 144.5, 140.6, 136.6,
135.6, 132.8, 130.1, 128.9, 128.4, 128.1, 127.1, 126.7,
126.0, 125.6, 124.4, 54.7, 34.2, 14.2, 12.7; IR m(C@O)
1705 cmꢀ1; HRMS for C21H18O: Calc. 286.1358, obsd.
286.1363.
4.2. 4,9-Dimethyl-2-phenyl-4,9-epoxycyclopenta[b]-
naphthalen-1-one (1a)
To a 100 mL high-pressure reactor were added
oxabenzonorbornadiene (1.3 g, 9.1 mmol), phenyl acety-
lene (0.50 mL, 4.6 mmol), 30 mL of CH2Cl2, and
Co2(CO)8 (78 mg, 0.23 lmmol). After the solution was
flushed with CO gas in several seconds, the reactor
was pressurized with 30 atm of CO. The reactor was
heated at 130 ꢁC for 18 h. After the reactor was cooled
to rt and excess gas was relieved, the solution was trans-
ferred into a flask and then evaporated to dryness. The
residue was chromatographed on a silica gel column
eluting with hexane and ethyl acetate (v/v, 8:1). Yield:
92%; 1H NMR (CDCl3): d7.76 (d, J = 3.0 Hz, 1H),
7.72 (m, 2H), 7.40–6.90 (m, 7H), 3.06 (dd, J = 5.1,
2.9 Hz, 1H), 2.57 (d, J = 5.1 Hz, 1H), 1.89 (s, 3H),
1.84 (s, 3H); 13C NMR (CDCl3): d204.2, 155.5, 148.5,
147.6, 131.3, 128.7, 128.4, 127.3, 127.2, 126.9, 125.8,
118.2, 118.1, 85.8, 85.1, 57.5, 52.6, 14.7, 14.4; IRm
4.5. 4,9-Dimethyl-2-phenylbenz[f]indene (1d)
To a 50 mL schlenk flask filled with nitrogen in an
ice-bath were added
a
solution of 1c (0.28 g,
0.98 mmol) in 15 mL of THF and LiAlH4 (23 mg,
0.59 mmol). The resulting solution was allowed to
warm to rt. After the solution was stirred for 4 h, sev-
eral drops of sat. aqueous NH4Cl solution were
added. As the NH4Cl solution was added, fluorescence
was disappeared. The resulting solution was filtered
over a MgSO4 pad and the filtrate was evaporated
to dryness. The residue was used further reactions
without further purification. To a 100 mL round-bot-
tom flask were added the residue, MgSO4 (5.0 g),
and 60 mL of hexane. After the resulting solution
was refluxed, the solution was filtered, evaporated,
and chromatographed on a silica gel column eluting
with hexane and ethyl acetate (v/v, 24:1). Yield:
70%; 1H NMR (CDCl3): d8.03 (m, 2H), 7.69 (d,
J = 7.2 Hz, 2H), 7.49 (s, 1H), 7.47 (m, 2H), 7.40
(C@O) 1698 cmꢀ1
;
302.1307, obsd. 302.1306.
HRMS for C21H18O2: Calc.
4.3. 4,9-Dimethyl-2-phenylbenz[f]inden-1-one (1b)
To a 100 mL of round-bottom flask was added 1a
(0.50 g, 1.8 mmol). To the solution was added MeOH
and hydrochloric acid (2 mL of HCl in 30 mL of
MeOH). After the resulting solution was refluxed for
5 h, the solution was cooled to rt. To the solution
were added ice water and saturated aqueous NaOH.
Ethyl acetate was added to extract organic com-

D.H. Kim et al. / Journal of Organometallic Chemistry 690 (2005) 1822–1828
1827
(t, J = 7.8 Hz, 2H), 7.28 (t, J = 7.3 Hz, 1H), 3.81 (s,
2H), 2.73 (s, 3H), 2.64 (s, 3H); 13C NMR (CDCl3):
d146.1, 141.9, 138.9, 136.2, 132.8, 131.5, 128.8,
127.8, 125.9, 125.8, 124.9, 124.6, 124.3, 123.1, 38.4,
15.3, 15.0; HRMS for C21H18: Calc. 270.1409, obsd.
270.1405.
C18H14ZrCl2: C, 55.09; H, 3.60. Found: C, 54.75; H,
3.64%.
4.9. Benz[f]indenylpentamethylcyclopentadienyl-
zirconium dichloride (5)
The reaction procedure was exactly the same as the
synthesis of 2 except the use of benz[f]indene instead
1
of 4,9-dimethyl-2-phenylbenz[f]indene. Yield: 46%. H
4.6. (4,9-Dimethyl-2-phenylbenz[f]indenyl)cyclo-
pentadienylzirconium dichloride (1)
NMR (C6D6): d8.44 (s, 2H), 7.91 (d, J = 6.7 Hz, 1H),
7.90 (d, J = 6.7 Hz, 1H), 7.30 (d, J = 6.7 Hz, 1H), 7.29
(d, J = 6.7 Hz, 1H), 6.37 (d, J = 3.3 Hz, 2H), 6.33 (t,
J = 3.2 Hz, 1H), 2.03 (s, 15H); Anal. Calc. for
C23H24ZrCl2: C, 59.72; H, 5.23. Found: C, 59.56; H,
5.52%.
To a 50 mL schlenk filled with nitrogen was added
solution of 4,9-dimethyl-2-phenyl-benz[f]indene
a
(0.1 g, 0.37 mmol) in THF (8 ml). The solution was
cooled by a dry ice/acetone bath. After n-BuLi
(0.15 ml, 2.5 M in hexane) was added at ꢀ78 ꢁC, the
solution was allowed to warm to rt. After the solution
was stirred for 1 h, the solution was evaporated to
dryness. To the residue were added CpZrCl3 (97 mg,
0.37 mmol) and 6 ml of toluene. The resulting solution
was stirred overnight. During the stirring, the solution
became red. After the solvent was removed, the resi-
due was dissolved in dichloromethane, filtered, and
dried. The residue was redissolved in toluene and
recrystallized by diffusion of Et2O at ꢀ20 ꢁC. Red
crystalline solids were obtained as a product. Yield:
70%. 1H NMR (C6D6): d8.24 (d, J = 6.9 Hz, 1H),
8.22 (d, J = 6.9 Hz, 1H), 7.77 (d, J = 7.0 Hz, 1H),
7.76 (d, J = 7.0 Hz, 1H), 7.53–7.39 (m, 5H), 7.09 (s,
2H), 5.99 (s, 5H), 3.04 (s, 6H); Anal. Calc. for
C26H22ZrCl2: C, 62.89; H, 4.47. Found: C, 63.22; H,
4.52%.
4.10. Benz[f]indenylindenylzirconium dichloride (6)
The reaction procedure was exactly the same as the
synthesis of 3 except the use of benz[f]indene instead
of 4,9-dimethyl-2-phenylbenz[f]indene. Yield: 45%.
1H NMR (CD2Cl2): d8.14 (s, 2H), 7.76 (d, J = 6.6 Hz,
1H), 7.75 (d, J = 6.6 Hz, 1H), 7.54 (d, J = 6.6 Hz,
1H), 7.53 (d, J = 6.6 Hz, 1H), 7.29 (d, J = 6.6 Hz, 1H),
7.28 (d, J = 6.6 Hz, 1H), 7.19 (d, J = 6.6 Hz, 1H), 7.18
(d, J = 6.6 Hz, 1H), 6.62 (t, J = 3.4 Hz, 1H), 6.44 (t,
J = 3.3 Hz, 1H), 6.25 (d, J = 3.4 Hz, 2H), 6.12 (d,
J = 3.3 Hz, 2H); Anal. Calc. for C22H16ZrCl2: C,
59.72; H, 3.64. Found: C, 59.41; H, 3.59%.
4.11. Ethylene polymerization
In a dry box, to a dried 70 ml glass reactor was
added 30 ml toluene. Activated complex, prepared by
mixing a complex (0.29 lmol) and MAO (0.492 g,
Al/Zr = 5000), was added to the reactor. The reactor
was assembled and brought out from the dry box.
The reactor was immersed in an oil bath whose tem-
perature had been set to 60 ꢁC and stirred for 5 min,
at which time the solution temperature reached to
the bath temperature. Ethylene was fed under the
pressure of 60 psig for 5 min. During feeding ethylene,
the reaction temperature went up to 70–72 ꢁC. Poly-
merization was quenched by venting ethylene gas
and pouring the mixture to acetone. Polyethylene
was precipitated from acidified methanol, filtered,
washed with methanol, and dried under vacuum at
50 ꢁC. White precipitates were collected by filtration
and dried under vacuum.
4.7. (4,9-Dimethyl-2-phenylbenz[f]indenyl)indenyl-
zirconium dichloride (3)
The reaction procedure was exactly the same as the
synthesis of 1 except the use of (Ind)ZrCl3 instead of
CpZrCl3. Yield: 50%. 1H NMR (CDCl3): d8.04 (d,
J = 6.9 Hz, 1H), 8.03 (d, J = 6.9 Hz, 1H), 7.81 (d,
J = 7.0 Hz, 1H), 7.80 (d, J = 7.0 Hz, 1H), 7.47 (m,
2H), 7.42 (m, 2H), 7.31–7.18 (m, 5H), 6.90 (m, 2H),
6.60 (s, 2H), 5.77 (m, 1H), 2.54 (s, 6H); Anal. Calc.
for C30H24ZrCl2: C, 65.92, H, 4.43. Found: C, 66.31;
H, 4.72%.
4.8. Benz[f]indenylcyclopentadienylzirconium dichloride
(4)
The reaction procedure was exactly the same as the
synthesis of 1 except the use of benz[f]indene instead
1
of 4,9-dimethyl-2-phenylbenz[f]indene. Yield: 63%. H
4.12. Crystallographic studies
NMR (CD2Cl2): d8.21 (s, 2H), 7.79 (d, J = 6.3 Hz,
1H), 7.78 (d, J = 6.3 Hz, 1H), 7.29 (d, J = 6.6 Hz, 1H),
7.28 (d, J = 6.6 Hz, 1H), 7.04 (t, J = 3.3 Hz, 1H), 6.64
(d, J = 3.3 Hz, 2H), 6.05 (s, 5H); Anal. Calc. for
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

1828
D.H. Kim et al. / Journal of Organometallic Chemistry 690 (2005) 1822–1828
methods (SHELXS-97) [11] and refined against all F2
data (SHELXS-97). All non-hydrogen atoms were
refined with anisotropic thermal parameters. The hydro-
gen atoms were treated as idealized contributions.
CCDC reference number 247504.
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(b) J.A. Ewen, R.W. Strozier, R.L. Jones Jr., M.J. Elder, PCT Int.
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Acknowledgments
Muller, J. Am. Chem. Soc. 118 (1996) 2291;
¨
(f) G. Rodriguez, G.C. Bazan, J. Am. Chem. Soc. 119 (1997)
343;
We thank the Ministry of Commerce, Industry, and
Energy of Korea. D.H.K. and J.A.L. are grateful for a
Brain Korea 21 fellowship.
(g) S. Trofimenko, Chem. Rev. 93 (1993) 943.
[4] G.W. Coates, Chem. Rev. 100 (2000) 1223.
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[6] P. Foster, J.C.W. Chien, M.D. Rausch, Organometallics 15
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