The effect that 6-tert-butoxyhexyl functionalization has on ethylene polymerization in ansa-zirconocene dichlorides

Article abstract of DOI:10.1016/j.jorganchem.2003.10.006

Ethylene polymerization studies have been carried out with novel precatalysts of the type: [(η⁵-C₁₃ H₈)-X(t-BuOC₆H₁₂)Me-(η⁵- C₅H₄)]ZrCl₂ [X=C [1a], Si [2a]], [(η⁵-C₁₃H₈)-XMe₂- (η⁵-(t-BuOC₆H₁₂C₅ H₃))] ZrCl₂ [X=C [3a], Si [4a]] in the presence of excess methylalumoxane (MAO) to compare their catalytic activity and to delineate the effect of the 6-t-butoxyhexyl functionality on ethylene polymerization. The precatalysts [1a] and [2a] with the bridge functionality showed higher activity in ethylene polymerization than the corresponding complexes [3a] and [4a] which have it on the Cp ring moiety. On the other hand the silyl bridged complexes [2a] and [4a] produced a higher molecular weight polyethylene than the carbon-bridged one, regardless of the location of functional group.

Full text of DOI:10.1016/j.jorganchem.2003.10.006

Journal of Organometallic Chemistry 689 (2004) 214–223
www.elsevier.com/locate/jorganchem
The effect that 6-tert-butoxyhexyl functionalization has
on ethylene polymerization in ansa-zirconocene dichlorides
*
Hyosun Lee , Choong Hoon Lee
LG Chemical Ltd./Research Park, 104-1 Munji-dong, Yuseong-gu, Daejon-city 305-380, Republic of Korea
Received 21 August 2003; accepted 2 October 2003
Abstract
New ansa-zirconocene dichloride derivatives have been prepared, which have a 6-t-butoxyhexyl pendant introduced either on a
Cp-ring-carbon or at the silicon and carbon ansa-bridging atom. Ethylene polymerization studies have been carried out with novel
precatalysts of the type: [(g5-C13H8)-X(t-BuOC6H12)Me-(g5-C5H4)]ZrCl2 [X ¼ C [1a], Si [2a]], [(g5-C13H8)-XMe2-(g5-(t-
BuOC6H12C5H3))] ZrCl2 [X ¼ C [3a], Si [4a]] in the presence of excess methylalumoxane (MAO) to compare their catalytic activity
and to delineate the effect of the 6-t-butoxyhexyl functionality on ethylene polymerization. The precatalysts [1a] and [2a] with the
bridge functionality showed higher activity in ethylene polymerization than the corresponding complexes [3a] and [4a] which have it
on the Cp ring moiety. On the other hand the silyl bridged complexes [2a] and [4a] produced a higher molecular weight polyethylene
than the carbon-bridged one, regardless of the location of functional group.
Ó 2003 Elsevier B.V. All rights reserved.
Keywords: Ansa-zirconocene; Fluorenyl; 6-t-Butoxyhexyl pendant; Ethylene polymerization; MAO
1. Introduction
ancillary on the Cp ring in an ansa-metallocene to deter-
mine the role that this constraint plays on the stereoreg-
ularity of a-olefin polymerization.
A large variety of ansa-metallocene precursors have
been synthesized, characterized and used industrially, not
only for the purpose of a-olefin polymerization catalysts
[1], but also for systematic mechanistic studies [2] since
Kaminsky coworkers [3] discovered catalytic a-olefin
polymerization by metallocene complexes in the presence
of methylalumoxane (MAO). Silyl-bridged cyclopenta-
dienyl (Cp)-fluorenyl (Flu) ligand based metallocenes [4],
along with half-sandwich metallocenes of ‘‘constrained
geometry’’ catalysts (CGCs) [5], are especially attractive
with respect to producing high molecular weight poly-
ethylene, microstructure-controlled polypropylene, and
a-olefin copolymers [6]. However, regarding these studies,
most metallocene precatalysts have been designed with a
dialkylsilyl or diarylsilyl bridging unit [7], or a pendant
hydrocarbyl or aryl group attached to one of the Cp rings
to monitor the steric and electronic effects of such sub-
stitution [8]. Marks and coworkers [9] introduced a chiral
Recently, Jutzi et al. [10,11] reported a functionalized
cyclopentadienyl complex which shows intra- or inter-
molecular donor–acceptor interaction between the
functional group and the metal center. Specifically, the
[Me2Si]-bridged (Cp)–(Flu) zirconocene containing an –
(CH2)2NR2 (R ¼ methyl or isopropyl) pendant group on
the Cp ring, with MAO as the cocatalyst, has produced
a bimodal polyethylene (a mixture of high and low
molecular weight polymers) by the presence of two
catalytically active sites, i.e., the metal center and the N-
donor functionality interacting with MAO [12].
A large number of group 4 metallocenes and ansa-
metallocenes have been reported with an –OR or –
(CH2)nOR functional group on the side chain [13,14],
which participates in metal binding as a hemi-labile li-
gand. However, examples of metallocenes in which
the –OR functional groups on the bridging unit or Cp
pendants in silicon and/or carbon-bridged (Cp)–(Flu)
zirconocenes have not been reported to date (Scheme 1).
In this paper we report the synthetic preparations of new
* Corresponding author. Tel.: +82428662758; fax: +82428613647.
E-mail address: hyobone@lgchem.com (H. Lee).
0022-328X/$ - see front matter Ó 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2003.10.006

H. Lee, C.H. Lee / Journal of Organometallic Chemistry 689 (2004) 214–223
215
Scheme 1. New ansa-zirconocene dichlorides with 6-t-butoxyhexyl pendant groups.
ansa-metallocene complexes and the activities of these
precatalysts in ethylene polymerization with MAO, to
better understand the effect of O-donor pendant arm
location.
group was introduced at the carbon and silicon bridge of
(Cp)(Flu)zirconium dichlorides in Schemes 2 and 3, re-
spectively. Schemes 4 and 5 illustrate the routes to pre-
pare the ansa-(Cp)(Flu)zirconium dichlorides with the
corresponding Cp-ring pendant group.
The syntheses of all substituted complexes were very
sensitive to the purity of the ligand dianion salt, sol-
vents of metallation, reaction temperature and reaction
time. Washing the dianion salt with hydrocarbon sol-
vent, after generating the dianion with two equivalents
n-BuLi in diethyl ether or THF, was very important in
the success of this preparation. Another reason for
washing the dilithium salt of the ansa-bridged ligand is
that more polar solvents lead to decomposition in the
metallation step. All excess THF needs to be removed;
this is effected by washing and subsequent trituration.
During the metallation step, hydrocarbon solvents such
as pentane or hexane were used as the reaction solvent
for the carbon bridged complexes; for the silicon-
bridged complexes, the metallation was found best to
be performed in diethyl ether. Shorter reaction times
and low temperature proved to be the best conditions
for this metallation as well. For the preparation of
carbon-bridged complexes, the intermediate fulvene
compounds were employed efficiently [18]. Complexes
[Me(t-BuOC6H12)C(Flu)(Cp)]ZrCl2 [1a] and [Me(t-
BuOC6 H12)Si(Flu)(Cp)]ZrCl2 [2a] were both obtained
as a racemic mixture. Enantiomeric and diastereo-
meric species are possible for complexes 1a–4a, due to
the presence of one or two stereogenic centers involv-
ing the bridging atom and Cp ring; all of the appro-
priate diastereomers were identified by 1H NMR
spectroscopy.
2. Results and discussion
2.1. Preparation and characterization of complexes [1a]–
[4a]
We have synthesized various metallocene catalyst
precusors that have a functional pendant arm on the
ancillary ligand in order to attach them to a modified or
unmodified silica surface [15]. Thus, the heterogenized
catalysts [16] can be delivered to a slurry or gas-phase
process free of ‘‘reactor fouling’’ in industry. Previously
mentioned, the ansa-metallocene complexes of group 4,
especially [dialkylsilyl(Cp)(Flu)] and [isopropyl-
ene(Cp)(Flu)] zirconium complexes have been used as
precatalysts to produce high molecular weight polyeth-
ylene and stereoregulated polypropylene [17] with rea-
sonable catalytic activity. With these advantages in
zirconocene chemistry, however syntheses of these ansa-
metallocene derivatives are not trivial. Such obstacles
for use of these complexes on an industrial scale include,
multiple steps in preparing pure ligands, difficulty in li-
gand purification and sensitivity to polar reaction sol-
vents such as THF during metallation step with the
desired ligand. These difficulties generally lead to low
preparative yields. The syntheses of ansa-zirconocene
dichlorides, with the functional pendant, 6-t-but-
oxyhexyl is illustrated in Scheme 2. The 6-t-butoxyhexyl

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H. Lee, C.H. Lee / Journal of Organometallic Chemistry 689 (2004) 214–223
Scheme 2. Synthesis of [Me(t-BuOC6H12)C(Flu)(Cp)]ZrCl2 [1a].
Scheme 3. Synthesis of [Me(t-BuOC6H12)Si(Flu)(Cp)]ZrCl2 [2a].
Scheme 4. Synthesis of [Me2C(Flu)(t-BuOC6H12Cp)]ZrCl2 [3a].
Compared to the ansa-metallocene complexes 1a and
the parent complex [Me2Si(Cp)(Flu)]ZrCl2 towards de-
composition.
2a that have the functionality to the bridge unit, the
corresponding metallocene 3a and 4a with the side chain
functionality more easily decompose. In addition all new
complexes have shown an increased solubility in hy-
drocarbon solvent compared to the parent complexes
that have no functional pendant. However, the metal-
locenes 2a and 4a appear to be much more stable than
2.2. Poymerization of ethylene with MAO
Ethylene polymerization was carried out with com-
plexes 1a–4a in combination with MAO at 60 °C in
toluene under ethylene pressure (30 psi). To ensure re-

H. Lee, C.H. Lee / Journal of Organometallic Chemistry 689 (2004) 214–223
217
Scheme 5. Synthesis of [Me2Si(Flu)(t-BuOC6H12Cp)]ZrCl2 [4a].
producibility, these polymerizations were repeated twice
for each catalyst precursor, summarized in Table 1. The
polyethylene that is produced by 1a–4a was analyzed by
gel permeation chromatography (GPC). Exceptionally,
complex 2a demonstrated the highest polyethylene
productivity among the rest of the catalysts by 2–4 fold.
Precatalysts 1a and 2a showed higher activity in ethylene
polymerization than the corresponding complexes 3a
and 4a. Furthermore, the silyl-bridged metallocenes
produced higher molecular weight polyethylene (Mw=Mn
value) than the carbon-bridged analog did, regardless of
whether the pendant was attached to the Cp ring or to
the bridge. Although this phenomenon has already been
observed in other catalyst systems, determining the de-
gree of electronic richness or poorness imparted to the
metal center by the Cp-type ligand [19,20], as well as
discovering the relationship between the electron density
of the metal center and the nature of the resulting
polymer are both ongoing challenges [21,22].
Ansa-bridges with single-atom linkers were demon-
strated as having an electron withdrawing effect through
experiment and calculations [23], thus ansa-bridges
[Me(t-BuOC6H12)Si] and [Me(t-BuOC6H12)C] are be-
lieved to possess some degree of an electron withdrawing
effect. The other apparent difference between complex 1a
and 2a is the size of the bridging atom. A comparison of
the crystal structures of parent complexes [Me2Si
(Cp)(Flu)]ZrCl2 and [Me2C(Cp)(Flu)]ZrCl2 reveals that
the geometry at the carbon atom is more tetrahedral
than for that of silicon [24]. Also, the amount that the
Cp or Flu group coordination is leaning from g5 coor-
dination towards g5 coordination is similar in the two
structures. Specifically, the Cp(cent)-Zr-Flu(cent) angles
in [Me2Si(Cp)(Flu)]ZrCl2 and [Me2C(Cp)(Flu)]ZrCl2
are 128° and 119°, respectively. These facts suggest the
ligand [Me2Si(Cp)(Flu)] may be able to better donate
electron density to the metal center than [Me2C(Cp)(-
Flu)] can, which may influence the kind of polyethylene
that is formed.
The polydispersities (Mw=Mn, PDI) of 2 or 3 for
polyethylene, which is characteristic of single site me-
tallocene catalysts, indicated that these precatalyst pro-
duced polyethylene with unimodal molecular weight
distribution at the polymerization temperature 60°C.
This observation is quite different from that involving
complexes in which there is an N-donor functional
group anchored to the Cp moiety such as in [Me2Si(g5-
(Pri2NC2H4)C5H3)2]ZrCl2 and the more closely related
complex,
[(g5-C13H8)-Me2C-(g5-(Et2NC2H4)C5H3)]
ZrCl2, which shows PDI values of about 18 and 15 in
which the shoulder of GPC curve occurs at 60 and
50 °C, respectively [12].
3. Conclusion
In summary, we have synthesized four new ansa-
zirconocene dichlorides which have a 6-t-butoxyhexyl
Table 1
Ethylene polymerization resultsa for [(g5-C13H8)-X(t-BuOC6H12)Me-(g5-C5H4)]ZrCl2 [X ¼ C [1a], Si [2a]] and [(g5-C13H8)-XMe2-g5-((t-
BuOC6H12)C5H3))] ZrCl2 [X ¼ C [3a], Si [4]]
Complex
Yield (g)
Time (min)
Mw
606,000
Mw=Mn
Activityb
1a
2a
3a
4a
6.76
4.46
4.30
4.40
30
8
2.8
3.0
2.5
2.7
4.5
11.2
2.9
1,208,000
478,000
998,000
30
30
2.9
a Polymerization conditions: zirconocene: 3 lmol, Al/Zr ¼ 1000, toluene 200 mL, Tp ¼ 60 °C, P ¼ 30 psi.
b Activity in 103 kg PE/mol of Zr h.

218
H. Lee, C.H. Lee / Journal of Organometallic Chemistry 689 (2004) 214–223
pendant introduced at the ring-carbon or at the silicon
and carbon ansa-bridge. Also we studied their catalytic
activity for ethylene polymerization in the presence of
excess MAO. The precatalysts [1a] and [2a] with the
bridge functionality showed higher activity in ethylene
polymerization than the corresponding complexes [3a]
and [4a] which have it on the Cp ring moiety. Also, the
silyl bridged complexes [2a] and [4a] produced higher
molecular weight polyethylene than the carbon-bridged
one, regardless of the location of functional group. The
temperature dependence of the production of polyeth-
ylene with a bimodal molecular weight distribution is
very distinctive for the N-donor functionalized metal-
locene complexes; however it is not yet clear at this point
whether this same trend is true for the O-donor func-
tionalized metallocenes described here, and this is a
subject for further study.
7.26 ppm): 1.17 (t-BuO, 9H, s), 3.31 (t-BuOCH2, 2H, t,
3JH–H ¼ 6.5 Hz), 1.31, 1.41, 1.50 (CH2, MeC(OH)H,
13H, m), 3.75 (MeC(OH)H, sextet).
4.3. 8-t-Butoxy-2-octanone (2)
Oxalyl chloride (1.5 eq. with respect to DMSO, 18
mL, 0.21 mol) was added to DMSO (3 eq. with respect
to alcohol, 30 mL, 0.42 mol) in 150 mL anhydrous
methylene chloride at )78 °C. After the reaction mixture
was stirred at )60 °C for 30 min, this reagent was added
slowly to 8-t-butoxy-2-octanol (27.7 g, 0.14mol) in 50
mL methylene chloride in a 1 L round-bottom flask at
)60 °C. The reaction mixture was stirred at )60 °C for 3
h and was quenched by Et3N (102 mL, 0.73 mol, 3 eq. of
oxalyl chloride) at )40 °C. The mixture was stirred at
)40 °C for an additional 30 min at room temperature
giving a brown oil crude product. The crude product
was washed with water (2 ꢀ 100 mL) and concentrated
to give a brown liquid product that was vacuum (75 °C
at 600 mTorr) distilled to afford 20.1 g of pure product
4. Experimental
4.1. General techniques and reagents
1
(75%). H NMR (CDCl3, 7.26 ppm): 1.16 (t-BuO, 9H,
3
s), 3.30 (t-BuOCH2, 2H, t, JH–H ¼ 7 Hz), 2.40
All manipulations were performed using the combi-
nation of glove box, high vacuum, and Schlenk tech-
niques [25]. Solvents were purified and degassed by
standard procedures prior to use. All available reagents
were purchased commercially and used as received un-
less otherwise noted in the experimental procedure. El-
emental analyses were performed using a Perkin–Elmer
2400 CHN Elemental Analyzer. 1H NMR and 13C
NMR spectra were recorded on a Bruker Advance
400DRX spectrometer operating at 399.9 and 100.6
3
(CH3COCH2, 2H, t, JH–H ¼ 8 Hz), 2.11 (CH3CO, 3H,
s), 1.49 (CH2, 4H, m), 1.31 (CH2, 4H, m).
4.4. 6-Methyl-6-(6-t-butoxyhexyl)fulvene, Me(t-BuOC6
H12)C@(C5H4) (3)
To a solution of 8-t-butoxy-2-octanone (13.5 g, 0.067
mol) and cyclopentadiene (9.0 g, 0.14 mol) in dry meth-
anol (200 mL), pyrrolidine (12.5 mL, 0.15 mol) was ad-
ded at room temperature. The reaction mixture was
stirred overnight at room temperature. Acetic acid (12 g,
0.2 mol, in 200 mL water) was added to the reaction
mixture and stirred for 1 h. The reaction solution was
diluted with 300 mL of diethyl ether and 200 mL of water.
The organic layer was then extracted, washed with brine
(200 mL), dried over MgSO4, and concentrated in vacuo
to give orange oil as a crude product. Pure pale yellow
product (6.5 g) was obtained by vacuum distillation (100
1
MHz, respectively. H NMR and 13C NMR chemical
shifts are reported in ppm relative to SiMe4 ðd ¼ 0Þ and
were referenced internally, relative to the protio solvent
impurity (d ¼ 7:26 ppm and d ¼ 77:0 ppm for CDCl3).
All coupling constants are reported in hertz. Gel per-
meation chromatography (GPC) for the polyethylene
was obtained using a Waters 150C plus apparatus in
1,2,4-trichlorobenzene at 140 °C. Calibration was per-
formed by narrow distributed linear polystyrene
standards.
1
°C and ca. 500 mTorr) (39%). H NMR (CDCl3, 7.26
ppm): 1.17 (t-BuO, 9H, s), 3.31 (t-BuOCH2, 2H, t,
3JH–H ¼ 7 Hz), 2.53 (CH3CpCH2, 2H, t, 3JH–H ¼ 7.6 Hz),
2.20 (CH3Cp, 3H, s), 6.52–6.47 (Cp, 4H, m), 1.40–1.30
(CH2, 4H, m), 1.60–1.52 (CH2, 4H, m).
4.2. 8-t-Butoxy-2-octanol (1)
t-Butoxyhexylmagnesium chloride in diethyl ether
(200 mL, ca. 0.14 mol) was slowly added to a diethyl
ether solution of acetaldehyde (20 mL, 0.36 mol) in a 1 L
3-neck round-bottom flask at 0 °C. After stirring the
reaction mixture at room temperature for 5 h, it was
quenched with 1 N HCl solution. The crude product was
extracted with diethyl ether (2 ꢀ 100 mL). The clear li-
quid product was dried over MgSO4 and concentrated
in vacuo to afford 27.7 g of the product (98% based on
4.5. 2-Methyl-20-6-t-butoxyhexylmethylene[cyclopentadie-
nyl-fluorene-9-yl], [(CpH)Me(t-BuOC6H12)C(FluH)] (4)
The above fulvene derivative (3) (6.5 g, 0.026 mol) in
THF (50 mL) was added to fluorenyllithium (1 Et2O
bound: 6.5 g, 0.026 mol) in THF (100 mL) at )78 °C
slowly. TLC (developing solvent EtOAc:hexane ¼ 5:95 v/
v%) was carried to confirm reaction completion after the
1
0.14 mol of the Grignard reagent). H NMR (CDCl3,

H. Lee, C.H. Lee / Journal of Organometallic Chemistry 689 (2004) 214–223
219
red reaction mixture was stirred at room temperature
4.7. 6-t-Butoxyhexyldichloromethylsilane (5)
overnight. The reaction mixture was quenched by a
saturated solution of NH4Cl (30 mL) and followed by
adding 300 mL water. A yellow crude product was ex-
tracted with diethyl ether and then purified by column
chromatography (silica, starting with 100% hexane, after
fluorene separation, with 10% EtOAc and 90% hexane)
A solution of t-butoxyhexylmagnesium chloride (ca.
100 mL, 0.14 mol in diethyl ether solution) was added to
the solution of trichloromethylsilane (24.7 mL, 0.21
mol) in hexane (100 mL) dropwise at )100 °C over 3 h.
The clear solution was filtered and the solid residue was
extracted with additional hexane after stirring at room
temperature for 3 h. The solvent was removed in vacuo
to get rid of excess trichloromethylsilane and to give 32 g
1
to give 10.5 g of the product as a yellow oil (97%). H
NMR (CDCl3, 7.26 ppm): 1.19 (t-BuO, 9H, s), 0.58, 0.89
(MeC, 3H, s), 1.90 (CH2, 2H, m), 1.49 (CH2, 2H, m),
1.30 (CH2, 4H, m), 1.27 (CH2, 2H, m), 3.31 (t-BuOCH2,
1
of colorless product (ca. 84%). H NMR (CDCl3, 7.26
3
2H, t, JH–H ¼ 7 Hz), 6.88, 6.62, 5.87 (CpH,
ppm): 0.75 (Si–Me, 3H, s), 1.17 (t-BuO, 9H, s), 3.55 (t-
BuOCH2, 2H, t, 3JH–H ¼ 8 Hz), 1.51 (CH2, 4H, m), 1.40
(CH2, 4H, m), 1.13 (Si–CH2, 2H, m).
3H, brs), 3.07 (methyleneCpH, 2H, brs), 4.15 (FluH, 1H,
s), 7.72 (FluH, 1H, m), 7.67 (FluH, 1H, m), 7.55 (FluH,
1H, m), 7.36 (FluH, 1H, m), 7.28 (FluH, 1H, m), 7.24
(FluH, 1H, m), 7.04 (FluH, 1H, m), 6.76 (FluH, 1H, m).
4.8. 6-t-Butoxyhexylchloromethyl-(9-fluorenyl)silane, (t-
BuOC6H12)MeSi(FluH)Cl (6)
4.6. 2-Methyl-20-6-t-butoxyhexylmethylene[cyclopenta-
dienyl-fluorene-9-yl]-zirconocenedichloride, [(g5-C13H8)-
Me(t-BuOC6H12)C-(g5-C5H4)]ZrCl2 (1a)
A solution of solid fluorenyllithium (1 Et2O bound: 7
g, 0.028 mol) in hexane (150 mL) was added to a solu-
tion of Me(t-BuOC6H12)SiCl2 (7.71 g, 0.028 mol) in
hexane (50 mL) dropwise at )78 °C over the period of 2
h. The reaction solvent was dried in vacuo after stirring
at room temperature for 5 h. The solid residue was ex-
tracted with hexane (100 mL) to give a pale yellow oil
product. 1H NMR (CDCl3, 7.26 ppm): 0.12 (Si–Me, 3H,
n-BuLi (1.6 M hexane solution, 10 mL, 0.016 mol)
was added slowly to
a
solution of [(t-BuOC6
H12)MeC(FluH)(CpH)] (4) (3.2 g, 0.008 mol) in THF
(50 mL) at )78 °C. After stirring the red reaction mix-
ture at room temperature for 5 h, the solvent was re-
moved in vacuo. A crude red solid was washed with
hexane (2 ꢀ 30 mL) to give 3 g of the dianion [(t-
BuOC6H12)MeC(Flu)(Cp)]Li2 (88%) that is used for the
next metallation step. This ligand solution of [(t-
BuOC6H12)MeC(Flu)(Cp)]Li2 (2.5 g, 0.0044 mol) in
hexane (50 mL) was added to the solution of ZrCl4 (1.02
g, 0.0045 mol) in hexane (50 mL) at )78 °C. The reac-
tion solvent was removed after stirring at room tem-
perature for 12 h. The solid residue was dried and
extracted with toluene 100 mL using a frit. The bright
red solid was washed with 10 mL of hexane to give 0.8 g
3
d), 1.18 (t-BuO, 9H, s), 3.28 (t-BuOCH2, 2H, t, JH–H
¼ 8 Hz), 1.46 (CH2, 4H, m), 1.27 (CH2, 4H, m), 1.0 (Si–
CH2, 2H, m), 4.12 (FluH, 1H, s), 7.88–7.85 (FluH, 2H,
m), 7.67–7.66 (FluH, 2H, m), 7.41–7.38 (FluH, 2H, m),
7.35–7.33 (FluH, 2H, m).
4.9. 6-t-Butoxyhexylmethyl-(cyclopentadienyl)-(9-flu-
orenyl)silane, [(CpH)(t-BuOC6H12)MeSi(FluH)] (7)
A solution of solid cyclopentadienyllithium (2.02 g,
0.028 mol) in THF (50 mL) was slowly added to a mixture
of (t-BuOC6H12)MeSi(FluH)Cl (11.2 g, 0.028 mol) in
THF (50 mL) at room temperature. The solvent was
pumped off after stirring at room temperature for 3 h. The
solid residue was extracted with hexane (100 mL) to give
an orange oily product (11.5 g, 95%). 1H NMR (CDCl3,
7.26 ppm): 1.17, 1.15 (t-BuO, 9H, s), )0.15, )0.36 (MeSi,
3H, s), 0.35, 0.27 (CH2, 2H, m), 0.60, 0.70 (CH2, 2H, m),
1.40, 1.26 (CH2, 4H, m), 1.16, 1.12 (CH2, 2H, m), 3.26 (t-
1
of pure product (31%). H NMR (CDCl3, 7.26 ppm):
1.18 (t-BuO, 9H, s), 2.39 (MeC, 3H, s), 1.82 (CH2, 2H,
m), 1.59 (CH2, 4H, m), 1.46 (CH2, 2H, m), 1.22 (CH2,
3
2H, m), 3.34 (t-BuOCH2, 2H, t, JH–H ¼ 7 Hz), 6.33
3
(CpH, 2H, t, JH–H ¼ 2 Hz), 5.80–5.75 (CpH, 2H, m),
7.27 (FluH, 2H, m), 7.56 (FluH, 2H, m), 7.63 (FluH,
1H, d, 3JH–H ¼ 9 Hz), 7.82 (FluH, 1H, d, 3JH–H ¼ 9 Hz),
8.14 (FluH, 2H, m). 13C NMR (CDCl3, 77 ppm): 27.5
(Me3CO, q, 1JC–H ¼ 124 Hz), 27.6 (MeC, q, 1JC–H ¼ 124
Hz), 44.4 (Me3C, s), 26.3 (MeC, s), 72. (ipsoC, s), 78.9
(ipsoC, s), 115.0, 122.1, 123.3, 123.6 (4C, s), 61.5
3
BuOCH2, 2H, t, JH–H ¼ 7 Hz), 2.68 (methyleneCpH,
2H, brs), 6.60, 6.52, 6.10 (CpH, 3H, brs), 4.10, 4.00
(FluH, 1H, s), 7.86 (FluH, 2H, m), 7.78 (FluH, 1H, m),
7.53 (FluH, 1H, m), 7.43–7.22 (FluH, 4H, m).
1
(Me3COCH2, t, JC–H ¼ 139 Hz), 40.6 (ipsoCCH2, t,
1
1JC–H ¼ 124 Hz), 30.6, 30.0, 26.6, 23.5 (4C, t, JC–H
¼
4.10. 6-t-Butoxyhexylmethylsilanediyl[cyclopentadienyl-
fluorene-9-yl]-zirconocenedichloride, [(g5-C13H8)-Me(t-
BuOC6H12)Si-(g5-C5H4)]ZrCl2 (2a)
124 Hz, 3JC–H ¼ 10 Hz), 101.6, 102.5, 118.7, 119.7, 129.3,
129.1, 125.2, 125.0, 124.9, 124.8, 123.4, 122.9 (FluC and
1
3
CpC, 12C, d, JC–H ¼ 171 Hz, JC–H ¼ 10 Hz). Analysis
calculated for C30H36OZrCl2: C, 62.69; H, 6.31. Found:
C, 61.33; H, 5.97%.
n-BuLi (1.6 M of hexane, 35 mL, 0.056 mol) was
added slowly to a solution of [(t-BuOC6H12)MeSi-

220
H. Lee, C.H. Lee / Journal of Organometallic Chemistry 689 (2004) 214–223
(FluH)(CpH)] (7) (12 g, 0.028 mol) in THF (100 mL) at
)78 °C. After stirring the red reaction mixture at room
temperature for 4 h, the solvent was removed in vacuo.
A crude orange solid was washed with hexane (2 ꢀ 50
mL) to give 10 g of dianion [(t-BuOC6H12)MeSi(Flu)
(Cp)]Li2 that is used for the next metallation (81%). The
ligand solution of [(t-BuOC6H12)MeSi(Flu)(Cp)]Li2 (2
g, 0.0045 mol) in a diethyl ether (30 mL) was added to
the solution of ZrCl4 (1.05 g, 0.0045 mol) in diethyl
ether (30 mL) at )78 °C. The reaction solution was fil-
tered after stirring at room temperature for 3 h and the
solid residue was extracted with CH2Cl2 (50 mL) using a
frit. The dark red solid was washed with 10 mL hexane
to give 1.44 g of pure product (54%). 1H NMR (CDCl3,
7.26 ppm): 1.19 (t-BuO, 9H, s), 1.13 (MeSi, 3H, s), 1.79
(CH2, 4H, m), 1.60 (CH2, 4H, m), 1.48 (CH2, 2H, m),
3.35 (t-BuOCH2, 2H, t, 3JH–H ¼ 7 Hz), 6.61 (CpH, 2H, t,
mol) was added slowly at )78 °C. The reaction mixture
was stirred at room temperature overnight. Acetic acid
(18 g, 0.3 mol, in 200 mL water) was then added to the
reaction mixture and stirred for an hour. The reaction
solution was diluted with 300 mL diethyl ether and 200
mL water and the organic layer was extracted. The or-
ganic layer was washed with brine (200 mL), dried over
MgSO4, and concentrated in vacuo to give an orange oil
crude product. 15.9 g of orange oil product was ob-
tained by vacuum distillation (110 °C, 500 mTorr)
1
(59%). H NMR (CDCl3, 7.26 ppm): 1.18 (t-BuO, 9H,
s), 2.14 (Me2C, 3H, s), 3.32 (t-BuOCH2, 2H, t, 3JH–H ¼ 7
Hz), 1.54 (CH2, 4H, m) 1.35 (CH2, 4H, m), 2.38
3
(CpCH2, 2H, t, JH–H ¼ 7.6 Hz), 6.49 (CpH, 1H, m),
6.35 (CpH, 1H, m), 6.16 (CpH, 1H, m).
4.13. 2-(6-t-Butoxyhexylcyclopentadienyl)-2-(fluorenyl)
propane, [(t-BuOC6H12CpH)Me2C(FluH)] (10)
3
3JH–H ¼ 3 Hz), 5.76 (CpH, 2H, d, JH–H ¼ 3 Hz), 8.13
(FluH, 1H, m), 7.83 (FluH, 1H, m), 7.78 (FluH, 1H, m),
7.65 (FluH, 1H, m), 7.54 (FluH, 1H, m), 7.30 (FluH,
2H, m), 7.06 (FluH, 1H, m). 13C NMR (CDCl3, 77
The above fulvene derivative (9) (8 g, 0.03 mol) in
THF (50 mL) was added slowly to fluorenyllithium (1
Et2O bound: 10 g, 0.041 mol) in THF (100 mL) at )78
°C. TLC (developing solvent EtOAc:hexane ¼ 5:95 v/
v%) was carried out to confirm reaction completion af-
ter the red reaction mixture was stirred at room tem-
perature overnight. The reaction mixture was quenched
by first adding a portion of a saturated solution of
NH4Cl (20 mL), followed by adding a portion of water
(200 mL). A yellow crude product was extracted with
diethyl ether and then purified by column chromatog-
raphy (silica, starting with 100% hexane, after fluorene
separation with 10% EtOAc and 90% hexane) to give 9.0
g of yellow oil as the pure final product (70%). 1H NMR
(CDCl3, 7.26 ppm): 1.19, 1.20 (t-BuO, 9H, s), 1.06, 1.05,
1.02 (Me2C, 6H, s), 1.27 (CH2, 2H, m), 1.41 (CH2, 2H,
m), 1.58 (CH2, 4H, m), 2.50, 2.46, 2.36 (Cp–CH2, 2H,
1
ppm): 27.5 (Me3CO, q, JC–H ¼ 124 Hz), )3.3 (MeSi, q,
1JC–H ¼ 121 Hz), 64.6, 66.7, 72.4, 103.3, 127.6, 128.4,
1
129.0 (7C, s), 61.4 (Me3COCH2, t, JC–H ¼ 135 Hz),
1
14.5 (ipso SiCH2, t, JC–H ¼ 122 Hz), 33.1, 30.4, 25.9,
1
22.7 (4C, t, JC–H ¼ 119 Hz), 110.7, 111.4, 125.0, 125.1,
128.8, 128.1, 126.5, 125.9, 125.3, 125.1, 125.0, 123.8
1
3
(FluC and CpC, 12C, d, JC–H ¼ 171 Hz, JC–H ¼ 10
Hz). Analysis calculated for C29H36OSiZrCl2: C, 58.96;
H, 6.14. Found: C, 58.68; H, 6.27%.
4.11. 6-t-Butoxyhexylcyclopentadiene (t-BuOC6H12CpH)
A clear liquid 6-t-butylhexylchloride (305 g, 1.58 mol)
was added to a solution of lithium cyclopentadienylide
(814 mL, 1.63 mol, 2.0 M of THF solution) dropwise at
0 °C. The reaction was exothermic and kept at ice bath
temperature for 2 h and stirred overnight at room
temperature. The reaction mixture was transferred into
a separatory funnel and washed with water (3 ꢀ 300 mL)
to give a red burgundy solution. The reaction solvent
was pumped off and the residue was vacuum distilled
(120 °C, 600 mTorr) to give a clear oily product (300 g,
83%). 1H NMR (CDCl3, 7.26 ppm): 1.18 (t-BuO, 9H, s),
1.45 (CH2, 2H, m), 1.35 (CH2, 4H, m), 1.53 (CH2, 4H,
m), 2.35 (CH2, 2H, m), 3.32 (t-BuOCH2, 2H, t,
3JH–H ¼ 7 Hz), 6.00 (CpH, 1H, brs), 6.15 (CpH, 1H,
brs), 6.32 (CpH, 1H, brs), 6.40 (CpH, 1H, brs), 2.94
(CpH, 1H, brs), 2.87 (CpH, 1H, brs).
3
t,3JH–H ¼ 7 Hz), 3.36 (t-BuOCH2, 2H, d of t, JH–H ¼ 7
Hz), 6.53, 6.10, 6.00, 5.97, 5.69 (CpH, 5H, brs), 3.07
(methyleneCpH, 2H, brs), 4.14, 4.11, 4.10 (FluH, 1H, s),
7.70 (FluH, 2H, m), 7.33 (FluH, 2H, m), 7.23–7.10
(FluH, 4H, m).
4.14.
Isopropylidene[3-(6-t-butoxyhexyl)-cyclopenta-
dienyl-fluoren-9-yl]-zirconocenedichloride, [(g5-C13H8)-
Me2C-(g5-(t-BuOC6H12C5H3))]ZrCl2 (3a)
n-BuLi (1.6 M of hexane, 26.3 mL, 0.042 mol) was
slowly added to a solution of [Me2C(FluH)(t-BuOC6
H12CpH)] (10) (9.0 g, 0.021 mol) in THF (200 mL) at )78
°C. After stirring the red reaction mixture at room tem-
perature for 5 h, the solvent was removed in vacuo. A
crude red solid was washed with hexane (2 ꢀ 50 mL) to
give 11.1 g of the dianion [Me2C(Flu)(t-BuOC6H12
Cp)]Li2 that is used for the next metallation (90%). The
ligand solution of [Me2C(Flu)(t-BuOC6H12Cp)]Li2 (2.5
4.12. 6,6-Dimethyl-3-(6-t-butoxyhexyl)fulvene, Me2C@
C5H4(t- BuOC6H12)
To a solution of anhydrous acetone (14.7 mL, 0.2
mol) and t-butoxyhexylcyclopentadiene (22.3 g, 0.1 mol)
in a dried methanol (200 mL), pyrrolidine (21 mL, 0.25

H. Lee, C.H. Lee / Journal of Organometallic Chemistry 689 (2004) 214–223
221
g, 0.0042 mol) in pentane (50 mL) was added to the so-
lution of ZrCl4 (0.98 g, 0.0042 mol) in pentane (50 mL) at
)78 °C. The pentane was removed after stirring at room
temperature for 12 h. The solid residue was dried and
extracted into toluene (100 mL) by use of a frit. The pink
solid was washed with 10 mL hexane to give 1.55 g of pure
vacuo. The solid residue was extracted with hexane (100
mL) and the volatiles were pumped off to give a yellow
oil product (99%). H NMR (C6D6, 7.15 ppm): 1.09 (t-
BuO, 9H, s), )0.09, )0.13 (Me2Si, 6H, s), 1.25 (CH2,
2H, m), 1.24 (CH2, 2H, m), 1.41 (CH2, 4H, m), 2.25
(CpCH2, 2H, m), 3.23 (t-BuOCH2, 2H, d of t, 3JH–H ¼ 7
Hz), 6.35, 6.05, 5.70 (CpH, 5H, m, brs), 3.05 (meth-
yleneCpH, 2H, brs), 4.20, 4.00, 3.85 (FluH, 1H, s), 7.80
(FluH, 2H, m), 7.45 (FluH, 2H, m), 7.29–7.20 (FluH,
4H, m).
1
1
product (63%). H NMR (CDCl3, 7.26 ppm): 1.16 (t-
BuO, 9H, s), 2.35 (Me2C, 3H, s), 2.40 (Me2C, 3H, s), 1.46
(CH2, 4H, m), 1.27 (CH2, 4H, m), 1.20 (CH2, 2H, m), 2.52
(Cp–CH2, 2H, m), 3.27 (t-BuOCH2, 2H, t, 3JH–H ¼ 7 Hz),
3
5.43 (CpH, 1H, t, JH–H ¼ 3 Hz), 5.67 (CpH, 1H, t,
3
3JH–H ¼ 3 Hz), 6.01 (CpH, 1H, t, JH–H ¼ 3 Hz), 8.15
4.17.
Dimethylsilyl[3-(6-t-butoxyhexyl)-cyclopenta-
(FluH, 2H, m), 7.80 (FluH, 2H, m), 7.54 (FluH, 2H, m),
7.26 (FluH, 2H, m). 13C NMR (CDCl3, 77 ppm): 27.5
(Me3CO, q, 1JC–H ¼ 124 Hz), 15.3 (Me2C, q, 1JC–H ¼ 124
Hz), 40.4 (Me3C, s), 25.9 (Me2C, s), 68.1, 72.4, 78.8, 113.8,
122.6, 136.4, 142.0 (7C, s), 61.5 (Me3COCH2, t,
1JC–H ¼ 140 Hz), 65.8 (CpCH2, t, 1JC–H ¼ 138 Hz), 30.5,
dienyl-fluorene-9-yl]-zirconocenedichloride, [(g5-C13H8)-
SiMe2-(g5-(t-BuOC6H12C5H3))]ZrCl2 (4a)
n-BuLi (1.6 M of hexane, 20 mL, 0.032 mol) was
added slowly to a solution of [Me2Si(FluH)(t-BuO
C6H12CpH)] (7.12 g 0.016 mol) in diethyl ether (100 mL)
at )78 °C. After stirring the red reaction mixture at
room temperature for 12 h, the volatiles were removed
in vacuo to give a sticky red solid. The ligand solution of
[Me2Si(Flu)(t-BuOC6H12Cp)]Li2 (7.31 g, 0.016 mol) in
diethyl ether (50 mL) was added to the solution of ZrCl4
(3.73 g, 0.016 mol) in diethyl ether (30 mL) at )78 °C.
The reaction solution was filtered after stirring at room
temperature for 5 h and the solid residue was extracted
with CH2Cl2 (50 mL) using a frit. The orange solid was
washed with 10 mL hexane to give 2.4 g of pure product
1
29.7, 29.2, 27.6 (4C, t, JC–H ¼ 124 Hz), 103.0, 103.1,
117.2, 128.9, 128.2, 125.3, 124.9, 124.8, 123.4, 123.2, 123.1
(FluC and CpC, 11C d, 1JC–H ¼ 171 Hz, 3JC–H ¼ 10 Hz).
Analysis calculated for C31H38OZrCl2: C, 63.24; H, 6.51.
Found: C, 61.53; H, 6.40%.
4.15. Chlorodimethyl-(9-fluorenyl)silane, Me2Si(FluH)
Cl (11)
A solution of solid fluorenyllithium (1 Et2O bound :
9.64 g, 0.056 mol) in hexane (300 mL) was added to a
solution of Me2SiCl2 (16 mL, 0.13 mol) in hexane (100
mL) dropwise at )78 °C for 2 h. The reaction solvent
was dried in vacuo after stirring at room temperature for
5 h. The solid residue was extracted with hexane (100
1
(25%). H NMR (CDCl3, 7.26 ppm): 1.16 (t-BuO, 9H,
s), 1.11 (Me2Si, 3H, s), 1.13 (Me2Si, 3H, s), 1.43 (CH2,
4H, m), 1.25 (CH2, 4H, m), 2.45 (Cp–CH2, 2H, m), 3.26
3
(t-BuOCH2, 2H, t, JH–H ¼ 7 Hz), 5.41 (CpH, 1H, t,
3
3JH–H ¼ 3 Hz), 5.70 (CpH, 1H, t, JH–H ¼ 3 Hz), 6.28
3
(CpH, 1H, t, JH–H ¼ 3 Hz), 8.13 (FluH, 2H, m), 7.67–
1
mL) to give a pale yellow solid. H NMR (C6D6, 7.15
ppm): )0.08 (Me2Si, 6H, s), 3.77 (FluH, 1H, s), 7.67
7.49 (FluH, 4H, m), 7.29 (FluH, 2H, m). 13C NMR
1
(CDCl3, 77 ppm): 27.5 (Me3CO, q, JC–H ¼ 125 Hz),
3
(FluH, 2H, d, JH–H ¼ 8 Hz), 7.55 (FluH, 2H, d,
1
)3.3 (Me2Si, q, JC–H ¼ 121 Hz), 27.6, 66.3, 72.4, 102.6,
3
3JH–H ¼ 8 Hz), 7.23 (FluH, 2H, t, JH–H ¼ 8 Hz), 7.18
113.8, 128.8, 129.1, 141.9 (9C, s), 61.5 (Me3COCH2, t,
1JC–H ¼ 141 Hz), 30.5, 30.2, 30.0, 29.2, 25.9 (5C, t,
1JC–H ¼ 124 Hz), 111.6, 112.0, 119.7, 123.8, 123.9, 125.0,
126.3, 126.5, 128.0, 128.1, 128.7 (FluC and CpC, 11C d,
1JC–H ¼ 161 Hz, 3JC–H ¼ 10 Hz). Analysis calculated for
C30H38OSiZrCl2: C, 59.57; H, 6.33. Found: C, 59.32; H,
6.09%.
3
(FluH, 2H, t, JH–H ¼ 8 Hz).
4.16. t-Butoxyhexylcyclopentadienyl)(9-fluorenyl)dimethyl-
silane, [(t-BuOC6H12CpH)Me2Si(FluH)] (12)
n-BuLi (1.6 M of hexane, 10.2 mL, 0.016 mol) was
added to a solution of [(t-BuOC6H12)(CpH)] (3.64 g,
0.016 mol) in THF (30 mL) at )78 °C slowly. After
stirring the red reaction mixture at room temperature
for 4 h, the yellow solution turned into clear. The re-
action solvent was removed in vacuo to give an oil
product that was used for the next reaction without
further purification. A solution of t-butoxyhexylcyclo
pentadienyllithium in THF (50 mL) was added dropwise
to a solution of chlorodimethylfluorenylsilane (11) (4.14
g, 0.016 mol) in THF (50 mL) at room temperature.
After stirring a yellow reaction mixture at room tem-
perature for 4 h, the reaction solvent was removed in
4.18. General procedure for the polymerization of ethylene
A zirconocene complex (3 lmol) in toluene was
placed in a 500 mL glass reactor that is equipped with a
mechanical stirrer and pressure controller. After acti-
vating the precatalyst by MAO (Zr/Al ¼ 1:1000, 1.11
mL, 3.0 mmol Al, 8.2 wt% in toluene) dry toluene (200
mL) was added to the reactor. The reactor was placed in
a 60 °C oil bath for 2 min while it was degassed and
saturated with ethylene for 3 min without agitation. The
polymerization time was measured at the moment the

222
H. Lee, C.H. Lee / Journal of Organometallic Chemistry 689 (2004) 214–223
[6] (a) For reports of the copolymerization of ethylene and a-olefins,
see: W. Kaminsky, I. Beulich, M. Arndt-Rosenau, Macromol.
Symp. 173 (2001) 211;
stirring started. Ethylene feeding was constant (30 psi)
during the polymerization. The polymerization was
terminated by cutting ethylene feeding and adding
methanol. Additionally the polymer solution was
quenched by the addition of a portion of 1 N HCl so-
lution and was then filtered, washed with hexane and
acetone, and dried in vacuo.
(b) D. Ruchatz, G. Fink, Macromolecules 31 (1998) 4674;
(c) K.L. Margarete, R.M. Waymouth, Angew. Chem. Int. Ed. 37
(1998) 922.
[7] (a) For reports of ansa-metallocenes involving other heteroatom
bridge units such as BR, S, SnR2, and GeR2, see: D.S. Stelck, P.J.
Shapiro, N. Basickes, Organometallics 16 (1997) 4546;
(b) A.J. Bard, A.H. Cowley, J.K. Leland, G.J.N. Thomas, N.C.
Norman, P. Jutzi, C.P. Morley, E. Schluter, J. Chem. Soc. Dalton
Trans. (1985) 1303;
Acknowledgements
(c) S. Pitter, G. Huttner, O. Walter, L. Zsolnai, J. Organomet.
Chem. 454 (1993) 183;
We are very grateful to LG Chemical Ltd. Research
Center and also to the Analytical lab for NMR, CHN
analysis and GPC data collection. Dr. David G. Chur-
chill (Postdoctoral Fellow, UC Berkeley) was also very
helpful in the written preparation of this manuscript.
(d) W.A. Herrmann, M.J.A. Morawietz, H.-F. Herrmann, F.
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