Fulvene having substituents only on 1-, 4-, and 6-positions: A key intermediate for novel ansa-metallocene complexes

Article abstract of DOI:10.1016/S0022-328X(03)00388-7

A synthetic route for 1,4-dimethyl-6-phenylfulvene (4) and 1,4-dimethyl-6,6-diphenylfulvene (5), which are characteristic in that they have substituents only on 1-, 4-, and 6-positions, is developed. The synthetic route is straightforward from 2-bromo-3-m

Full text of DOI:10.1016/S0022-328X(03)00388-7

Journal of Organometallic Chemistry 677 (2003) 133ꢁ139
/
www.elsevier.com/locate/jorganchem
Fulvene having substituents only on 1-, 4-, and 6-positions: a key
intermediate for novel ansa-metallocene complexes
Young Chul Won a, Heon Yong Kwon a, Bun Yeoul Lee a,*, Young-Whan Park b
a Department of Molecular Science and Technology, Ajou University, Suwon 442-749, South Korea
b LG Chem Ltd., Research Park, 104-1, Munji-dong, Yuseong-gu, Daejon 305-380, South Korea
Received 3 April 2003; received in revised form 23 April 2003; accepted 6 May 2003
Abstract
A synthetic route for 1,4-dimethyl-6-phenylfulvene (4) and 1,4-dimethyl-6,6-diphenylfulvene (5), which are characteristic in that
they have substituents only on 1-, 4-, and 6-positions, is developed. The synthetic route is straightforward from 2-bromo-3-methyl-2-
cyclopenten-1-one ethylene ketal (1), which can be easily synthesized in 100-g scale. Overall yield from 1 is 50 and 47% for 4 and 5,
respectively. Synthesis of an ansa-metallocene complex, [Ph(H)C(fluorenyl)(1,3-Me2Cp)]ZrCl2 (7), is demonstrated using 4. Much
higher comonomer incorporation in ethylene/1-hexene copolymerization and dramatic increase of molecular weight in 1-hexene
polymerization are observed with 7 when the reactivity compared with that of the one not having methyl substituents,
[Ph(H)C(fluorenyl)(Cp)]ZrCl2.
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Fulvene; Metallocenes; Zirconium; Polymerization; Cyclopentadienyl
1. Introduction
pentamethylfulvene were developed and they were used
successfully for the syntheses of novel metallocene
complexes [7]. However, until now, synthetic route for
fulvenes having substituents only on 1-, 4-, and 6-
positions (I in Eq. (1)) has not been developed. Herein,
we disclose a synthetic route for these fulvenes. Synth-
esis of an ansa-metallocene complex is demonstrated
using the fulvene and its reactivities to the olefin
(co)polymerizations are studied. The ansa-metallocene
complexes derived from the fulvene are characteristic in
that substituents on the cyclopentadienyl ligand are
located adjacent to the bridge point [8]. With the
complexes, the steric congestion at the reaction site is
kept minimum, while electronic effect is controlled by
the substituents.
Various metallocene complexes, which can serve as
catalysts for the polymerization of olefins, can be
synthesized from fulvenes. Scheme 1 shows its versatility
[1]. Fulvenes are also substrates for cycloaddition
reaction by which useful organic compounds can be
provided [2,3]. Fulvenes are obtained by coupling
reaction of cyclopentadiene or substituted cyclopenta-
dienes with aldehydes or ketones [3,4]. When 1,3-
disubstituted cyclopentadiene is used, the substituents
are situated in 1,3-positions in the resulting fulvene by
steric reason (II in Eq. (1)) [5]. Other routes for fulvene
derivatives have been developed but, in those cases, the
products still have substituents on 1- and 3-positions [6].
Syntheses of 1,2,3,4-tetramethylfulvene and 1,2,3,4,6-
(1)
* Corresponding author. Tel.:
312191592.
ꢀ
/
82-312191844; fax:
ꢀ/82-
E-mail address: bunyeoul@ajou.ac.kr (B.Y. Lee).
0022-328X/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00388-7

134
Y.C. Won et al. / Journal of Organometallic Chemistry 677 (2003) 133ꢁ139
/
vatives; and (c) treatment with base to furnish fulvenes.
Overall yields for the second step are fairly good (72 and
69% for 4 and 5, respectively). Dehydration is carried
out simply by shaking ethyl acetate solution of the
generated tertiary alcohol with aqueous 2 N HCl for
several minutes [10]. The final reaction was conducted
by reacting the generated cyclopentadiene with NaOMe/
MeOH in THF. The appearance of red color indicates
the formation of fulvene and the structures are con-
firmed by 1H- and 13C-NMR spectra and elemental
analyses. Two vinyl proton signals at 6.03 and 6.10 ppm
(C6D6) and two methyl proton signals at 1.79 and 2.00
1
ppm are observed for 4 in H-NMR spectrum. A vinyl
proton signal at 6.05 ppm (CDCl3) and a methyl proton
signal at 1.40 ppm are observed for 5.
Scheme 1. Metallocene complexes from a fulvene.
2. Results and discussion
2.2. Synthesis of [Ph(H)C(fluorenyl)(1,3-
Me2Cp)]ZrCl2 (7)
2.1. Syntheses of 1,4-dimethyl-6-phenylfulvene (4) and
1,4-dimethyl-6,6-diphenylfulvene (5)
Synthesis of an ansa-metallocene complex is demon-
strated (Eq. (2)) using 4. Nucleophilic attack of fluor-
enyl anion to 4 gives the desired ligand 6 (86%). The
deprotonation of 6 with two equivalents of n-BuLi and
subsequent reaction of the resulting dianion with
ZrCl4(THF)2 in pentane afford clearly the desired
ansa-zirconocene complex 7 as red solid (77%). Two
A fulvene having substituents only on 1-, 4-, and 6-
positions are synthesized by the route shown in Scheme
2. Starting material 1 can be easily synthesized in 100-g
scale from commercially available 3-methyl-2-cyclopen-
ten-1-one by two steps. The novel route consists of two
steps. The first step is composed of four individual
reactions: (a) lithiation of 1 with n-BuLi; (b) addition of
a ketone or an aldehyde; (c) deprotection of ketal group;
and (d) protection of the generated hydroxyl group. It
can be conducted in one pot with overall high yields (70
and 68% for 2 and 3, respectively). Deprotection of ketal
group is carried out successfully by treatment of
aqueous 1 N HCl briefly. In the case of addition of
benzaldehyde, the generated secondary alcohol can be
protected with tetrahydropyranyl (THP) without pro-
blems but, in the case of addition of benzophenone, a
tertiary alcohol is generated which is difficult to be
protected with THP group [9]. Protection even to methyl
ether by NaH/methyl iodide condition is not successful.
The protection problem can be overcome by transform-
ing the generated lithium alkoxide in the second reaction
directly to methyl ether by the addition of methyl iodide.
The deprotection of ketal is carried out after the
formation of methyl ether.
CpÃ
/
H signals are observed separately at 6.02 and 6.06
1
3.6 Hz) in H-NMR spectrum due
ppm as doublet (Jꢂ
/
to destroyed symmetry by the phenyl group. Signal of
proton attached on bridge carbon is observed at 6.25
ppm as singlet. Methyl proton signals are observed at
1.72 and 1.84 ppm as singlet. Fulvene 5 is inert to the
nucleophilic attack of fluorenyl anion.
ð2Þ
Single crystals suitable for X-ray crystallography are
obtained by vapor phase addition of pentane to a
benzene solution. Fig. 1 shows the ORTEP drawing of 7
with selected bond lengths and angles. Cp(centroid)Ã
/
ZrÃfluorenyl(centroid) angle, the value of which indi-
/
The second step is composed of three individual
reactions: (a) 1,2-addition of methyllithium to the
carbonyl; (b) dehydration to give cyclopentadiene deri-
cates how far the zirconium atom displaces from the
cyclopentadienyl and fluorenyl ligand, is 118.88. The
value is slightly bigger than that observed for
[Ph2C(Cp)(fluorenyl)]ZrCl2 (117.68) [11] indicating that
the Zr atom in [Ph2C(Cp)(fluorenyl)]ZrCl2 is located
slightly further out of the mouth of the ligand. The angle
of ClÃ
/
ZrÃCl (98.77(10)8) is slightly bigger than that of
/
[Ph2C(Cp)(fluorenyl)]ZrCl2 (95.98). Methyl substituents
are slightly above the cyclopentadienyl plane. Dihedral
Scheme 2. (i) n-BuLi, ꢃ
HCl for 2 (or MeI for 3); (iv) dihydropyrane, p-TsOH for 2 (or 1 N
/
78 8C; (ii) RCOPh (RꢂH or Ph); (iii) 1 N
/
angles of C21Ã
/
C19Ã
/
C18Ã
/
C17 and C20Ã
/
C16Ã
/
C17Ã/C18
HCl for 3); (v) MeLi; (vi) 2 N HCl; and (vii) NaOMe/THF.
are ꢃ172.58 and 173.88, respectively.
/

Y.C. Won et al. / Journal of Organometallic Chemistry 677 (2003) 133ꢁ
/
139
135
tically by the methyl substituents. The polymer obtained
with 7 is rubbery solid (Mw, 1 050 000) while that
obtained by the comparison catalyst 8 is oily (Mw,
100 000). Capability to control tacticity is not reduced
severely in this case as well ([rrrr], 83 and 87% for 7 and
8, respectively). Almost same 13C-NMR spectra are
observed for both copolymers. In ethylene/1-hexene
copolymerization, rather lower molecular weight and
lower activity are observed with complex 7 (entries 7 and
8) but 1-hexene incorporation is increased dramatically.
Complex 7 produces a copolymer having 15 mol% 1-
hexene content while complex 8 gives a copolymer
having only 4.0 mol% 1-hexene content under the
same polymerization condition. In the ethylene/norbor-
nene copolymerization, both complexes show the similar
reactivity in terms of activity, norbornene content, and
molecular weight.
Fig. 1. ORTEP view of 7, showing the atom numbering scheme.
Thermal ellipsoids are shown at 30% probability level. Hydrogen
˚
atoms have been omitted for clarity. Selected bond distances (A) and
angles (8): ZrÃ
ZrÃC(2), 2.554(9); ZrÃ
2.488(11); ZrÃC(17), 2.533(11); C(14)Ã
1.523(12); C(16)ÃC(20), 1.532(13); C(19)Ã
Zr(1)ÃCl(2), 98.77(10); C(1)ÃC(14)ÃC(15), 101.6(7); Cp(centroid)Ã
Zr(1)ÃCp(centroid), 117.15.
/
Cl(1), 2.412(3); ZrÃ
C(7), 2.659(8); ZrÃ
C(15), 1.527(12); C(1)Ã
/
Cl(2), 2.421(3); ZrÃ
/
C(1), 2.401(9);
/
/
/
C(15), 2.447(9); ZrÃ
/C(16),
/
/
/C(14),
/
/
C(21), 1.518(12); Cl(1)Ã
/
/
/
/
/
/
2.3. Polymerization studies
3. Conclusion
The complex was tested in ethylene, propylene, 1-
hexene, ethylene/1-hexene, and ethylene/norbornene
(co)polymerizations. The reactivity is compared with
that of an ansa-zirconocene complex not having methyl
substituents, [PhCH(fluorenyl)(Cp)]ZrCl2 (8) [12], to
investigate the effects of the methyl substituents. In the
ethylene and propylene polymerizations, rather lower
activity and lower molecular weight are observed with 7
A synthetic route for 1,4-dimethyl-6-phenylfulvene (4)
and 1,4-dimethyl-6,6-diphenylfulvene (5), which are
characteristic in that they have substituents only on 1-,
4-, and 6-positions, is developed and synthesis of an
ansa-metallocene complex, [Ph(H)C(fluorenyl)(1,3-
Me2Cp)]ZrCl2 (7), is demonstrated using 4. When the
polymerization reactivity of 7 is compared with that of
the one not having methyl substituent, [Ph(H)C(fluor-
enyl)(Cp)]ZrCl2 (8), molecular weight (Mw) is increased
by 10 times in 1-hexene polymerization and incorpora-
tion of 1-hexene is increased dramatically in ethylene/1-
hexene copolymerization. Various fulvenes and hence
various novel metallocene complexes are expected to be
synthesized by using the synthetic route described in this
paper. We are currently studying the syntheses and
(entries 1ꢁ4 in Table 1). Capability to control tacticity is
/
not reduced by the methyl substituents in propylene
polymerization. Both catalysts give syndiotacticity-rich
poly(propylene) having almost same Tm (139 and 137 8C
for 7 and 8, respectively) and [r] content (65 and 66% for
7 and 8, respectively). In 1-hexene polymerization
(entries 5 and 6), molecular weight is increased drama-
Table 1
Polymerization results
Activity (kg molꢃ1 hꢃ1
)
Tm (8C)
Mw
Mw/Mn
a
a
Entry
Catalyst
Monomer
1
2
7
Ethylene
Ethylene
Propylene
Propylene
1-Hexene
1-Hexene
6.0
13.4
1.8
131
133
262000
302000
153000
210000
1050000
100000
90400
2.5
3.2
1.8
1.9
2.4
2.0
1.9
1.9
4.6
3.7
8 b
7
3
139
137
4
8
2.9
5.3
5
7
ND
ND
ND
113
121 e
122 e
6
8
7.7
7 c
8 d
9
7
Ethyleneꢀ
Ethyleneꢀ
Ethyleneꢀ
Ethyleneꢀ
/
1-hexene
13.9
25.3
139
130
8
/1-hexene
129000
404000
483000
7
/norbornene
10
8
/norbornene
ND, not detected.
a
Determined by GPC in 1,2,4-trichlorobenzene at 140 8C against polystyrene standards.
[PhCH(fluorenyl)(Cp)]ZrCl2.
15 mol% 1-hexene content by 13C-NMR study.
4.0 mol% 1-hexene content.
Tg value instead of Tm.
b
c
d
e

136
Y.C. Won et al. / Journal of Organometallic Chemistry 677 (2003) 133ꢁ139
/
polymerization reactivities of the metallocene com-
plexes.
solution was cooled to 0 8C. Concentrated aqueous
NaHCO3 solution (1.2 l) was added dropwise while
keeping the temperature below 5 8C. Vigorous evolution
of CO2 gas was detected. After solid NaHCO3 (ca. 100
g) was added additionally at 0 8C, the aqueous solution
became slightly basic and evolution of CO2 gas ceased.
Ether phase was collected and dried with MgSO4.
Removal of solvent with rotary evaporator gave a solid
which was dissolved in ethyl acetate (250 ml) and hexane
4. Experimental
4.1. General considerations
All manipulations were performed under an inert
atmosphere using standard glove box and Schlenk
techniques. Toluene, pentane, THF, diethyl ether, and
C6D6 were distilled from benzophenone ketyl. Anhy-
drous grade DMSO was purchased from Aldrich and
used without further purification. Toluene used for
polymerization reaction was purchased from Aldrich
(anhydrous grade) and purified further by distillation
(500 ml). When the solution was stored at ꢃ20 8C
/
overnight, white crystals were deposited, which were
collected by filtration (106 g). The solvent in the mother
liquor was removed by rotary evaporator. The residue
was dissolved in ethyl acetate (100 ml) and hexane (300
ml) again. Storing the solution at ꢃ20 8C overnight
/
gave the second crops (20 g). The total isolated yield was
1
50% (126 g). m.p. 54 8C. H-NMR (400 MHz, CDCl3,
over Naꢁ/K alloy. 1-Hexene was purified by distillation
over Naꢁ
/
K alloy. Norbornene was dissolved in toluene
(3.54 M) and the solution was purified by distillation
25 8C): dꢂ
2.68ꢁ
2.70 (m, 2 H, CH2) ppm. 13C{1H}-NMR (100
MHz, CDCl3, 25 8C): dꢂ19.02 (CH3), 32.19 (CH2),
33.25 (CH2), 122.73 (CÄC), 173.35 (CÄC), 201.10 (CÄ
O) ppm. IR (neat, KBr): n˜ CÃCÄ
1610 and 1710 (CÄ
O) cmꢃ1. C6H7BrO (175.03)*
Anal. Calc.: C, 41.2; H,
/
2.20 (s, 3 H, CH3), 2.54ꢁ2.56 (m, 2 H, CH2),
/
/
over NaꢁK alloy. Methylaluminoxane (MAO) was
/
/
purchased as a solution in toluene from Akzo (7.6
wt.% of Al, MMAO type 4). Ethylene and propylene
were purchased from Conley Gas (99.9%) and MG
industry, respectively, and purified by contacting with
molecular sieves and copper overnight under the pres-
sure of 150 psig. NMR spectra were recorded on a
Varian Mercury plus 400 spectrometer. Elemental
analyses were carried out on a Fisons EA1108 micro-
analyzer. IR spectra were recorded on Nicolet Magma-
IR 550. Gel permeation chromatograms (GPC) were
obtained at 140 8C in trichlorobenzene using Waters
/
/
/
/
ꢂ
/
/
/
/
/
4.04. Found: C, 41.0; H, 4.37%.
4.3. Bromoketal compound 1
2-Bromo-3-methyl-2-cyclopenten-1-one (93.0 g, 0.531
mol), ethylene glycol (230 g, 3.70 mol), and triethyl
orthoformate (235 g, 1.59 mol) were mixed in 1.0-l one
neck flask. p-Toluenesulfonic acid monohydrate (2.0 g)
was added and the solution was stirred for 4 h at room
temperature (r.t.). KOH (2.4 g) dissolved in 500 ml
water was added to the solution. The compound was
Model 150-Cꢀ GPC and the data were analyzed using a
/
polystyrene analyzing curve. Differential scanning ca-
lorimetry (DSC) was performed on a Thermal Analysis
3100. Compound 1 was reported but experimental
details and spectroscopic data are missing in the
literature [13]. We have developed 100-g scale synthesis
of the compound.
extracted with hexane (500 mlꢄ3). The volatiles were
/
removed by rotary evaporator. TLC study shows only
two spots, product and reactant. The reactant was
removed by solubility difference. The reactant is soluble
in water but sparingly soluble in hexane. The product is
soluble in hexane but insoluble in water. Thus, the
residue was dissolved in hexane (1.25 l) again and the
solution was poured into a 3.0-l separatory funnel. The
4.2. 2-Bromo-3-methyl-2-cyclopenten-1-one
3-Methyl-2-cyclopenten-1-one (142 g, 1.24 mol) was
dissolved in CCl4 (760 ml) in 3.0-l three neck flask. The
solution was cooled to 0 8C with an ice bath. Bromine
(260 g, 1.63 mol) dissolved in CCl4 (760 ml) was added
dropwise for 5 h while keeping the temperature below
5 8C. The solution should be stirred with mechanical
stirrer because thick slurry was formed. The liquid phase
was removed by cannula, a tip of which is capped with
filter paper, while keeping the temperature at 0 8C. CCl4
(250 ml) was added and the slurry was stirred. The liquid
phase was removed by the cannula again. This washing
process was repeated twice. The washing process should
be conducted in a hood because HBr gas was evolved
from the decanted solution. Diethyl ether (760 ml) was
added to dissolve the obtained yellow solid and the
solution was washed with distilled water (1.0 lꢄ10).
/
The hexane phase was dried briefly with minimum
amount of anhydrous MgSO4. The solvent was removed
by rotary evaporator. The residue was distilled under
full vacuum (500 mTorr, 65ꢁ70 8C) to give white solid
/
(93.5 g, 81%). Special care should be exerted during
distillation. The distillation temperature should be
lowered as far as possible. Decomposition of the
compound was observed when the bath temperature
was above 120 8C. The boiling temperature can be
lowered by connecting the glass joints with vacuum
grease and by cooling the collecting flask with dry ice/
acetone bath. The condenser should be cooled with
ambient air. The compound is solidified inside the

Y.C. Won et al. / Journal of Organometallic Chemistry 677 (2003) 133ꢁ
/
139
137
condenser if it was cooled with cooling water. m.p.
4.5. Compound 3
1
35 8C. H-NMR (400 MHz, CDCl3, 25 8C): dꢂ
3 H, CH3), 2.15ꢁ2.18 (m, 2 H, CH2), 2.34ꢁ2.37 (m, 2 H,
CH2), 3.93ꢁ4.00 (m, 2 H, OCH2), 4.13ꢁ4.21 (m, 2 H,
OCH2) ppm. 13C{1H}-NMR (100 MHz, CDCl3, 25 8C):
dꢂ16.53 (CH3), 32.85, 34.44, 65.66, 118.05, 118.74,
144.15 ppm. C8H11BrO2 (219.09)*Anal. Calc.: C, 43.9;
/1.80 (s,
To a Schlenk flask containing 1 (1.13 g, 5.20 mmol) in
THF (6.0 ml) was added n-BuLi at ꢃ78 8C (1.44 g, 2.5
M in hexane, 5.20 mmol) dropwise and the solution was
stirred for 1 h at ꢃ78 8C. A solution of benzophenone
(0.948 g, 5.20 mmol) in THF (1.0 ml) was added and the
solution was stirred for 2 h at ꢃ78 8C. The solution was
/
/
/
/
/
/
/
/
/
H, 5.07. Found: C, 44.2; H, 5.35%.
warmed to r.t. and the solvent was removed under
vacuum. DMSO (7.5 ml) and MeI (0.85 ml, 13.8 mmol)
were added successively. The solution was stirred over-
night. Aqueous saturated NH4Cl solution (1.0 ml) and
aqueous 1 N HCl solution (0.3 ml) was added succes-
sively. The mixture was stirred for 10 min. Aqueous
saturated NaHCO3 solution (4.0 ml) was added and the
4.4. Compound 2
To a Schlenk flask containing 1 (5.00 g, 23.0 mmol) in
THF (25 ml) was added n-BuLi at ꢃ78 8C (6.39 g, 2.5
M in hexane, 23.0 mmol) dropwise and the solution was
stirred for 1 h at ꢃ78 8C. Benzaldehyde (2.45 g, 23.0
mmol) was added and the solution was stirred for 2 h at
78 8C. The solution was poured into a separatory
funnel containing water (30 ml) and the product was
extracted with ethyl acetate (40 mlꢄ2). The combined
/
product was extracted with diethyl ether (8.0 mlꢄ5).
/
/
The product was dissolved in hot hexane and ethyl
acetate (v/v, 10:1). White crystals were obtained by
ꢃ
/
storing the solution in a freezer (ꢃ
68% (1.04 g). m.p. 130 8C. 1H-NMR (400 MHz, CDCl3,
25 8C): dꢂ2.29ꢁ2.36 (m, 2 H, CH2), 2.32 (s, 3 H, CH3),
2.48ꢁ2.51 (m, 2 H, CH2), 2.89 (s, 3 H, OCH3), 7.20ꢁ7.30
(m, 6 H, phÃH), 7.39ꢁ7.42 (m, 4 H, phÃH) ppm.
13C{1H}-NMR (100 MHz, CDCl3, 25 8C): dꢂ
19.70,
33.33, 35.02, 51.21, 84.93, 126.93, 127.37, 128.04,
141.09, 141.46, 173.69, 206.48 (CÄO) ppm. C20H20O2
(292.40)*Anal. Calc.: C, 82.1; H, 6.91. Found: C, 82.0;
H, 6.88%.
/
20 8C). Yield was
/
/
/
organic layer was shaken with 1 N aqueous HCl
solution (40 ml) for about 30 s, in which step the ketal
group was deprotected to furnish a carbonyl. The
organic layer was washed with concentrated aqueous
NaHCO3 solution (40 ml). The solution was dried over
anhydrous MgSO4 and the solvent was removed to give
a residue which was used for the next step without
further purification (yield: 96%). The residue was
dissolved in CH2Cl2 (50 ml) and dihydropyrane (4.85
g, 57.6 mmol) and p-toluenesulfonic acid monohydrate
(44 mg, 0.23 mmol) were added at r.t. The solution was
stirred for 2 h and then diluted with ethyl acetate (25
ml). The solution was washed with saturated aqueous
NaHCO3 solution. The organic phase was collected and
dried over anhydrous MgSO4. Removal of solvent by
rotary evaporator gave a residue which was purified by
column chromatography on silica gel eluting with
hexane and ethyl acetate (v/v, 3:1). Yield was 4.60 g
/
/
/
/
/
/
/
/
4.6. 1,4-Dimethyl-6-phenylfulvene (4)
To a Schlenk flask containing 2 (2.17 g, 7.57 mmol) in
diethyl ether (24 ml) was added MeLi (6.05 ml, 1.5 M in
diethyl ether, 9.08 mmol) at ꢃ78 8C dropwise. The
/
solution was allowed to warm to r.t. and stirred for 5 h.
Water (20 ml) was added. Diethyl ether was removed by
rotary evaporator. Ethyl acetate (60 ml) was added to
the residue and the mixture was poured into a separa-
tory funnel. The aqueous layer was removed and
aqueous 2 N HCl solution (40 ml) was added. The
mixture was shaken vigorously for 3 min. The aqueous
layer was removed and the organic layer was washed
with saturated aqueous NaHCO3 solution (40 ml). The
organic layer was collected and dried over anhydrous
MgSO4. Solvent was removed by rotary evaporator to
give a residue. To the residue were added NaH (0.19 g,
8.0 mmol) and THF (20 ml) under nitrogen atmosphere.
Methanol (2.0 ml) was added via syringe, upon which
hydrogen gas was evolved and the solution turned to
red. The solution was stirred for 3 h at r.t. under
nitrogen. The solution was poured into a separatory
funnel containing water (20 ml) and hexane (60 ml). The
organic layer was collected and dried over anhydrous
MgSO4. Removal of solvent gave a red residue which
was purified by column chromatography on silica gel
eluting with hexane and toluene (v/v, 10:1). Yield was
1
(overall 70%). Two diastereomers are observed in H-
1
NMR spectrum. H-NMR (400 MHz, CDCl3, 25 8C):
dꢂ
H, CH3), 2.32ꢁ
OCH2), 3.76ꢁ3.88 (m, 1 H, OCH2), 4.57 (dd, JH,H
2.9, 4.6 Hz, 0.5 H, OCHO), 4.64 (t, JH,H
H, OCHO), 5.78 (s, 0.5 H, PhCÃH), 5.82 (s, 0.5 H,
PhCÃH), 7.21ꢁ7.46 (m, 5 H, PhÃH) ppm. Spectral data
of the intermediate hydroxyl compound are as follows.
1H-NMR (400 MHz, CDCl3, 25 8C): dꢂ
2.10 (s, 3 H,
CH3), 2.35ꢁ2.45 (m, 2 H), 2.50ꢁ2.60 (m, 2 H), 4.58 (d,
3JH,H
9.1 Hz, 1 H, OCÃH), 5.59 (d, JH,H
H, OÃH), 7.20ꢁ7.36 (m, 5 H, phenylÃ
H) ppm. 13C{1H}-
NMR (100 MHz, CDCl3, 25 8C): dꢂ17.49 (CH3),
32.07, 34.58, 70.14 (CÃOH), 125.73, 127.44, 128.48,
140.04, 142.85, 172.18, 210.60 (CÄO) ppm. IR (neat): n˜
1639 and 1690 (CÄCÃCÄ
O), 3420 (br, OH) cmꢃ1
/
1.51ꢁ/1.74 (m, 6 H), 2.15 (s, 1.5 H, CH3), 2.27 (s, 1.5
/
2.41 (m, 2 H, CH2), 3.42ꢁ3.54 (m, 1 H,
/
3
/
ꢂ
/
3
ꢂ3.3 Hz, 0.5
/
/
/
/
/
/
/
/
3
ꢂ
/
/
ꢂ9.1 Hz, 1
/
/
/
/
/
/
/
/
ꢂ
/
/
/
/
.

138
Y.C. Won et al. / Journal of Organometallic Chemistry 677 (2003) 133ꢁ139
/
1
0.920 g (72%). H-NMR (400 MHz, C6D6, 25 8C): dꢂ
/
4.9. [Ph(H)C(fluorenyl)(1,3-Me2Cp)]ZrCl2 (7)
To a stirred solution of 6 (0.100 g, 0.287 mmol) in
1.79 (s, 3 H, CH3), 2.00 (s, 3 H, CH3), 6.03 (dq, 3JH,H
ꢂ
/
4
3.6, JH,H
ꢂ
/
2.0 Hz, 1 H, CH3Ã
/
CÄ
2.0 Hz, 1 H, CH3Ã
7.16 (m, 6 H) ppm. 13C{1H}-NMR (100 MHz, C6D6,
25 8C): dꢂ13.08 (CH3), 17.15 (CH3), 127.58, 127.94,
128.08, 129.59, 130.11, 132.70, 133.51, 134.03, 137.15,
147.24 ppm. C14H14 (182.28)*Anal. Calc.: C, 92.2; H,
7.76. Found: C, 92.0; H, 7.52%.
/
CH), 6.10 (dq,
3JH,H
ꢂ
/
3.6, JH,H
ꢂ
/
/
CÄCH), 7.03ꢁ
/
/
4
cold THF (3 ml, ꢃ30 8C) was added n-BuLi (0.159 g,
/
2.5 M in hexane, 0.574 mmol) dropwise. The solution
was stirred overnight. The solvent was removed by
vacuum and the residue was washed with pentane (4.0
ml) and benzene (4.0 ml). ZrCl4(THF)2 (0.108 g, 0.287
mmol) and pentane (5.0 ml) was added to the red
dilithium salt and the slurry was stirred for 24 h. The
solvent was decanted and the product was extracted
with benzene (ca. 12 ml). Removal of solvent gave a red
solid which is quite pure by the analysis of 1H- and 13C-
NMR spectra. Yield was 0.11 g (77%). The single
crystals suitable for X-ray crystallography and elemental
analysis were obtained by vapor phase addition of
pentane to a benzene solution overnight at r.t. 1H-
/
/
4.7. 1,4-Dimethyl-6,6-diphenylfulvene (5)
The compound was prepared according to the same
procedure and condition for 4. The product was purified
by column chromatography on silica gel eluting with
hexane and toluene (v/v, 10:1). Yield was 69%. m.p.
NMR (400 MHz, C6D6, 25 8C): dꢂ
/
1.72 (s, 3 H, CH3),
3.6 Hz, 1 H, CpÃH),
H), 6.25 (s, 1 H), 6.66
1
1.84 (s, 3 H, CH3), 6.02 (d, 3JH,H
ꢂ
/
/
98 8C. H-NMR (400 MHz, CDCl3, 25 8C): dꢂ
/
1.40 (s,
7.20 (m, 4 H,
H) ppm. 13C{1H}-NMR
(100 MHz, CDCl3, 25 8C): dꢂ16.92 (CH3), 127.75,
128.13, 130.54, 130.62, 132.39, 142.44, 144.32, 151.37
ppm. C20H18 (258.38)*Anal. Calc.: C, 93.0; H, 7.04.
3
6.06 (d, JH,H
6 H, CH3), 6.05 (s, 2 H, vinylÃ
/
H), 7.16ꢁ
/
ꢂ
/
3.6 Hz, 1 H, CpÃ
/
3
3
PhÃH), 7.27ꢁ7.31 (m, 6 H, PhÃ
/
/
/
(t, JH,H
7.02ꢁ7.20 (m, 5 H), 7.26 (t, JH,H
(dd, 3JH,H 6.4, 4JH,H 1.2 Hz, 2 H), 7.73 (dd, 3JH,H
8.4, 6.0 Hz, 2 H) ppm. 13C{1H}-NMR (100 MHz, C6D6,
25 8C): dꢂ16.51, 19.30, 41.67, 73.96, 99.41, 121.28,
ꢂ
/
7.6 Hz, 1 H), 6.91 (t, JH,H
ꢂ/7.6 Hz, 1 H),
3
/
/
ꢂ/7.2 Hz, 2 H), 7.45
ꢂ
/
ꢂ
/
ꢂ
/
/
Found: C, 93.1; H, 7.02%.
/
122.34, 122.66, 123.14, 123.70, 123.81, 123.99, 124.40,
124.82, 124.84, 124.92, 125.02, 126.27, 126.63, 126.70,
127.36, 128.35, 128.72, 138.45 ppm. C27H22Cl2Zr
4.8. Ligand 6
(508.56)*Anal. Calc.: C, 63.8; H, 4.37. Found: C,
/
63.5; H, 4.15%.
To a stirred solution of fluorene (0.162 g, 1.0 mmol) in
cold THF (5 ml, ꢃ30 8C) was added n-BuLi (0.277 g,
2.5 M in hexane, 1.0 mmol) dropwise inside a glove box.
The resulting solution was stirred for 1 h. Compound 4
/
4.10. Polymerization
In a dry box, to a dried 70-ml glass reactor was added
30 ml of toluene, 1-hexene, norbornene solution in
toluene (3.54 M), or 1-hexene solution in toluene (0.50
M). The reactor was assembled and brought out from
the dry box. The reactor was immersed in an oil bath
whose temperature had been set to a given value and
stirred for 15 min. An activated catalyst prepared by
mixing a given amount of catalyst and MAO was added
via a syringe. Ethylene or propylene was fed immedi-
ately under the predetermined pressure. After polymer-
ization had been conducted for a given time, it was
quenched by venting ethylene or propylene gas and
pouring the mixture to a solution of methanol and
concentrated aqueous HCl (v/v, 1:1). The resulting white
slurry was stirred for several hours. White precipitates
were collected by filtration, washed with methanol, and
dried under vacuum. Detailed conditions for each
polymerization reactions are as follows: 0.5 mmol
(0.182 g, 1.0 mmol) in THF (1.0 ml) was added at ꢃ
/
30 8C and the solution was stirred for 2 h at r.t.
Saturated aqueous NH4Cl solution (5 ml) was added
and the product was extracted with diethyl ether. The
collected organic layer was dried over anhydrous
MgSO4. Removal of solvent by rotary evaporator gave
a residue which was purified by column chromatogra-
phy on silica gel eluting with hexane and toluene (v/v,
1
20:1). Yield was 0.298 g (86%). m.p. 133 8C. H-NMR
(400 MHz, CDCl3, 25 8C): dꢂ
/
1.87 (s, 3 H, CH3), 1.92
(d, 4JH,H
ꢂ
/
1.6 Hz, 3 H, CH3), 2.81 (d, 3JH,H
ꢂ/2.0 Hz, 2
H, CH2), 3.80 (d, 3JH,H
ꢂ
/
11.6 Hz, 1 H, PhCÃ
/
H or FluÃ
/
3
H), 4.87 (d, JH,H
ꢂ
/
11.6 Hz, 1 H, PhCÃ
/
H or FluÃ
8.0 Hz, 1 H),
/
H),
3
5.87 (s, 1 H, vinylÃ
/
H), 6.48 (d, JH,H
7.2 Hz, 1 H), 7.0ꢁ7.4 (m, 9 H), 7.70 (d,
7.2 Hz, 2 H) ppm. 13C{1H}-NMR (100 MHz,
CDCl3, 25 8C): dꢂ15.22, 16.65, 44.43, 48.43, 48.51,
ꢂ
/
3
6.94 (t, JH,H
ꢂ
/
/
3JH,H
ꢂ
/
/
119.23, 119.36, 125.28, 125.80, 125.99, 126.11, 126.20,
126.36, 126.82, 126.90, 127.98, 129.38, 138.78, 140.82,
140.91, 141.57, 142.72, 144.02, 145.88, 146.30 ppm.
catalyst, Al/Zrꢂ
polymerization; 2.0 mmol catalyst, Al/Zrꢂ
psig, 20 min for propylene polymerization; 1.0 mmol
catalyst, Al/Zrꢂ4000, r.t., 30 min for 1-hexene poly-
merization; 0.5 mmol catalyst, Al/Zrꢂ4200, 75 psig,
/
4000, 60 8C, 75 psig, 6 min for ethylene
/
2000, r.t., 75
C27H24 (348.51)*/Anal. Calc.: C, 93.0; H, 6.96. Found:
/
C, 93.2; H, 7.07%.
/

Y.C. Won et al. / Journal of Organometallic Chemistry 677 (2003) 133ꢁ
/
139
139
60 8C, 10 min for ethylene/1-hexene copolymerization;
0.25 mmol catalyst, Al/Zrꢂ6000, 100 psig, 60 8C, 5 min
Acknowledgements
/
for ethylene/norbornene copolymerization. 13C-NMR
spectra of ethylene/1-hexene copolymers were recorded
at 100 8C with 708 flip angle, acquisition time of 1.5 s,
and a delay time of 4.0 s. The copolymers (ca. 80 mg)
were dissolved in a mixed solvent (0.5 ml) of C2D2Cl4
and C6H3Cl3 (v/v, 1:2). The 1-hexene contents were
calculated according to the literature method [14]. 13C-
NMR spectra of the poly(propylene) were recorded at
125 8C with 458 flip angle, acquisition time of 2.3 s, and
a delay time of 2.0 s. The copolymers (ca. 60 mg) were
dissolved in C2D2Cl4 (0.5 ml). The [r] contents were
calculated according to the literature method [15]. Table
1 summarizes the polymerization results.
The authors are grateful to LG Chemical Ltd. for
financial assistance and to Prof. Y.K. Chung and D.M.
Shin for the single crystal X-ray diffraction studies.
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/
254.28, aꢂ
/
˚
˚
˚
8.2574(7) A, bꢂ
106.437(4)8, bꢂ102.150(4)8, gꢂ
1.542 g cmꢃ3, triclinic, space group P1; crystal size
0.2ꢄ0.2ꢄ 293(2) K, scan type v/2u,
0.1 mm3, Tꢂ
1.405U 527.21, ꢃ95h 59, ꢃ105k 511, ꢃ175
l 519, 5515 measured reflections, 3501 independent
reflections (Rint 0.0954), mꢂ
0.758 mmꢃ1, R1 [F2ꢀ
2s(F2)]ꢂ
0.0542, wR2ꢂ0.1213.
/
9.1131(7) A, cꢂ
/
15.6296(16) A, aꢂ
/
/
/
92.759(4)8, Zꢂ
/
4, dꢂ
/
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¯
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ꢂ
/
/
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Chem. 587 (1999) 181;
5. Supplementary material
(b) B.Y. Lee, J.W. Han, I.S. Lee, Y.K. Chung, J. Organomet.
Chem. 627 (2001) 233.
Crystallographic data for structural analysis have
been deposited with the Cambridge Crystallographic
Data Center, CCDC No. 205363 for compound 7.
Copies of this information may be obtained free of
charge form The Director, CCDC, 12, Union Road,
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¨