C2-bridged metallocene dichloride complexes of the types (C13H8-CH2CHR-C9H 6-nR′n)ZrCl2 and (C13H8-CH2CHR-C13H 8)MCl2 (n=0, 1; R=H, alkenyl; R′=alkenyl, benzyl; M=Zr, Hf) as self-immobilizing catalyst precursors for ethylene polymerization

Article abstract of DOI:10.1016/S0022-328X(98)00736-0

A total of 15 C₂-bridged fluorenylidene indenylidene and bis(fluorenylidene) metal dichloride complexes (metal=Zr, Hf) and the corresponding ligand precursors have been prepared and characterized. ω-Alkenyl substituents with various chain lengths in the C₂-bridge or in position 3 of the indenylidene moiety have an impact on the polymerization activity of the catalysts and the molecular weights of the produced polyethylenes. These ω-alkenyl substituents cause 'self-immobilization' due to their incorporation into the backbone of a growing polymer chain providing heterogeneous catalyst systems.

Full text of DOI:10.1016/S0022-328X(98)00736-0

Journal of Organometallic Chemistry 580 (1999) 1–16
C2-bridged metallocene dichloride complexes of the types
(C13H8–CH2CHR–C9H6−nRn% )ZrCl2 and
(C13H8–CH2CHR–C13H8)MCl2 (n=0, 1; R=H, alkenyl; R%=alkenyl,
benzyl; M=Zr, Hf) as self-immobilizing catalyst precursors for
ethylene polymerization1
Helmut G. Alt *, Michael Jung
Laboratorium fu¨r Anorganische Chemie der Uni6ersita¨t Bayreuth, Postfach 10 12 51, D-95440 Bayreuth, Germany
Received 23 March 1998
Abstract
A total of 15 C2-bridged fluorenylidene indenylidene and bis(fluorenylidene) metal dichloride complexes (metal=Zr, Hf) and
the corresponding ligand precursors have been prepared and characterized. v-Alkenyl substituents with various chain lengths in
the C2-bridge or in position 3 of the indenylidene moiety have an impact on the polymerization activity of the catalysts and the
molecular weights of the produced polyethylenes. These ꢀ-alkenyl substituents cause ‘self-immobilization’ due to their incorpora-
tion into the backbone of a growing polymer chain providing heterogeneous catalyst systems. © 1999 Published by Elsevier
Science S.A. All rights reserved.
Keywords: Catalysis; Polymerization; Zirconium; Metallocene complexes
1. Introduction
dene ligand to investigate and compare their catalytic
ethylene polymerization activities. We were especially
interested in the influence of the position of the ꢀ-
alkenyl substituent on the polymerization properties of
the catalysts and the molecular weights of the produced
polyethylenes.
In the past 15 years metallocene complexes with
group 4 metals became established catalysts for the
polymerization of a-olefins [1–7]. ansa-Metallocene
complexes with a C2-bridge show very high catalytic
olefin polymerization activities [8,9]. The C2-bridge
causes a favorable dihedral angle between both aro-
matic ligands and it allows their sufficient mobility that
is advantageous for the kinetics of the olefin polymer-
ization. We synthesized C2-bridged fluorenylidene in-
denylidene and bis(fluorenylidene) metal dichloride
complexes (metal=Zr, Hf) with one v-alkenyl sub-
stituent in the bridge or in position 3 of the indenyli-
2. Results and discussion
2.1. Synthesis of the ꢀ-alkenyl oxiranes 1–3
No suitable synthesis was yet available for the substi-
tution of an ethylene bridge in ansa-metallocene com-
plexes with an alkenyl group. The synthetic route
described here offers a new method for the substitution
of a C2-bridge with an v-alkenyl substituent. The first
step is the one-sided epoxidation of a diene to form an
optically active alkenyl oxirane [10]. The respective
* Corresponding author. Fax: +49 921 552157.
1 Dedicated to Professor Dr. Gu¨nter Marx on the occasion of his
60th birthday (23.11.98).
0022-328X/99/$ - see front matter © 1999 Published by Elsevier Science S.A. All rights reserved.
PII S 0 0 2 2 - 3 2 8 X ( 9 8 ) 0 0 7 3 6 - 0

2
H.G. Alt, M. Jung / Journal of Organometallic Chemistry 580 (1999) 1–16
Table 1
NMR data of the alkenyl oxiranes 1–3 (250.13 MHz (1H), 69.2 MHz (13C))
1H-NMRa)
13C-NMRa)
5.68 (m, 1H,ꢀCH), 4.83 (m, 1H,ꢀCH2), 4.83 (m, 1H,ꢀCH2),
2.73 (ABMX2, 1H, CH), 2.54 (ABM, 1H, CH2), 2.27
(ABM, 1H, CH2), 2.05 (m, 2H, CH2), 1.45 (m, 2H, CH2)
137.6 (ꢀCH), 115.1 (ꢀCH2), 51.8 (CH),
47.1 (CH2), 31.8, 30.1 (CH2)
5.66 (m, 1H,ꢀCH), 4.81 (m, 1H,ꢀCH2), 4.81 (m, 1H,ꢀCH2),
2.77 ABMX2, 1H, CH), 2.60 (ABM, 1H, CH2), 2.32
(ABM, 1H, CH2), 1.94 (m, 2H, CH2), 1.43–1.31 (6H, CH2)b
138.3 (ꢀCH), 114.2 (ꢀCH2), 51.9 (CH),
46.6 (CH2), 33.4, 32.1, 28.4, 25.2 (CH2)
5.73 (m, 1H,ꢀCH), 4.86 (m, 1H,ꢀCH2), 4.86 (m, 1H,ꢀCH2),
2.80 (ABMX2, 1H, CH), 2.67 ABM, 1H, CH2), 2.40–2.36
(ABM, 1H, CH2), 1.95 (m, 2H, CH2), 1.45–1.27 (10H, CH2)b
138.8 (ꢀCH), 114.1 (ꢀCH2), 52.1 (CH),
46.8 (CH2), 33.6, 32.3, 29.1, 28.8, 28.7,
25.7 (CH2)
a)in CDCl3 (saturated solution) at 25°C; b)indicated as a shift range due to resonance overlap.
dienes are reacted with an equimolar amount of m-
chloroperbenzoic acid in methylene chloride to give the
1,2-epoxy alk-v-ene compounds 1–3. The NMR spec-
troscopic data of the epoxy alkenes 1–3 are listed in
Table 1 (Fig. 1).
2.3. Synthesis of C2-bridged ligand precursors of the
type C13H9–C2H4–C9H6R (R=alkyl, alkenyl)
A ligand precursor with an unsubstituted ethylene
bridge is obtained by the reaction of 2-(9-fluorenyl)-1-
bromoethane and indenyllithium or substituted indenyl-
lithium compounds. HMPT (hexamethylphosphoric
triamide) has to be added to avoid the formation of
4,5,6,7-dibenzospiro[2,4]heptane [15]. Using this reac-
tion pathway, several 1-indenes (i.e. allyl-1-indene, 3-
butenyl-1-indene, 4-pentenyl-1-indene, 5-hexenyl-1-
indene, benzyl-1-indene and 5-hexenyldimethylsilyl-1-
indene) were reacted to prepare C13H9–C2H4–C9H6R
ligand precursors according to known procedures [16]
(Scheme 1).
2.2. Synthesis of C2-bridged ligand precursors of the
types C13H8–CH2CHR–C9H7 and
C13H8–CH2CHR–C13H8 (R=H, alkenyl)
The 1,2-epoxy alkenes 1–3 react quantitatively with
fluorenyllithium by ring opening to form the corres-
ponding alcoholates or, after hydrolysis, to give the
corresponding alcohols 4/4*–6/6* [11–13]. The subse-
quent mesylation [14] of the alcohol with mesyl chloride
in dichloromethane in the presence of triethylamine
produces compounds 7/7*–9/9*. The compounds are a
mixture of isomers formed by addition of the fluorenyl-
lithium to the two methylene carbon atoms of the
oxirane. The isomer mixture is used for the further
reactions (Fig. 2). The NMR spectroscopic data of
compounds 4/4*–9/9* are given in Table 2.
The mesylates react with fluorenyllithium or indenyl-
lithium in a nucleophilic substitution to form the cor-
responding C2-bridged ligand precursors 10/10*–15/
15*. These reactions are relatively slow. Therefore, to
achieve high yields, the reaction mixtures are stirred for
4–5 days at room temperature. The isomers 10/10*–12/
12* could not be separated and were used without
separation for the subsequent complexation reactions
(Fig. 3).
Fig. 1. One-sided epoxidation of a, v-dienes.
Fig. 2. Reaction pathway for the isomer mixtures 7/7*–9/9*.

H.G. Alt, M. Jung / Journal of Organometallic Chemistry 580 (1999) 1–16
3
Scheme 2. Isomerization of the double bond by addition of HMPT.
Fig. 3. Ligand precursors 10/10*–15/15*.
4.47 ppm, as well as triplets at l=7.36, 7.25, 7.22, 7.21,
7.20, 7.08 and 7.06 ppm. These are attributed to the
aromatic protons of both fluorenylidene ligands. The
vinyl group signals appear as three multiplets at l=
5.86, 5.05 and 5.00 ppm. The protons of the ethylene
bridge form an AMX spin system whereby the proton
of the alkenyl group bonding carbon atom (=X part)
couples additionally with the neighboring methylene
group. The multiplet appears at l=5.16 ppm; the
AM-part forms a doublet of a doublet, each at l=4.65
and 4.24 ppm. The multiplets at l=2.42 and 2.09 ppm
are attributed to the two methylene groups of the
alkenyl chain.
The increase of the solvent polarity, due to the
addition of HMPT, causes an isomerization of the
double bond in the five-membered indenyl ring (Scheme
2). 2-(9-Fluorenyl)-1-bromoethane [15] reacts with the
corresponding substituted and lithiated indenyl deriva-
tives to form the ethylene bridged ligand precursors
16/16*–21/21*. The NMR spectroscopic data of com-
pounds 10/10*–21/21* are listed in Table 3 (Figs. 3 and
4).
2.4. Synthesis of the metallocene dichloride complexes
The bridged metallocene complexes 22/22*–35 were
synthesized in diethyl ether using standard procedures
[8,17]. The ligand precursor was mixed with n-butyl-
lithium, and the dianion formed was reacted with solid
zirconium tetrachloride or hafnium tetrachloride
(Scheme 3).
The J-modulated 13C-NMR spectrum of 25 (Fig.
8(b)) shows ten signals for the quaternary carbon atoms
at l=129.3, 128.4, 125.5, 124.4, 123.7, 123.6, 120.4,
120.1, 107.6 and 101.7 ppm and 16 signals for the
tertiary carbon atoms of both fluorenylidene ligands at
l=128.3, 128.2, 128.0, 127.7, 125.6, 125.4, 125.2,
125.2, 125.1, 124.8, 124.5, 124.3, 123.1, 123.0, 122.9 and
121.9 ppm. The signals at l=42.5 ppm (tertiary carbon
atom) and l=35.5 ppm (secondary carbon atom) are
attributed to the ethylene bridge. The signals at l=
34.8 and 32.3 ppm correspond to the two methylene
groups of the butenyl chain.
The quaternary carbon atoms 9 and 9% are located at
l=107.1 and 101.7 ppm in the region of a h5-bonded
fluorenylidene ligand [18–20]. In contrast, the signal of
the quaternary carbon atom in C1-bridged fluorenyli-
dene complexes appears at l=80 ppm corresponding
to a h3 bonding mode of the ligand. For the recently
The ethylene bridged bis(fluorenylidene) complexes are
fairly air stable. Fig. 5 provides an overview of the
metallocene complexes synthesized. Compounds 22/
22*–24/24* exist as a mixture of various isomers (Fig.
6). Therefore, no clear interpretation of the NMR-spec-
tra of these complexes was possible. The bis(fluorenyli-
dene) complexes 25–29 possess higher symmetry than
the mixed fluorenyl indenyl derivatives due to the two
identical p-ligands and exist as enantiomeric pairs (Fig.
1
7). Fig. 8(a) shows the H-NMR spectrum of 25. The
assignment of the signals in the 1H- and 13C-NMR
1
spectra was confirmed by a 250.13 MHz 2D-1H, H-
Cosy 45 experiment and a 62.9 MHz 2D-1H, 13C het-
eronuclear shift correlation experiment (Table 4). The
1H-NMR spectrum shows doublets in the aromatic
region at l=8.10, 8.02, 7.81, 7.79, 7.70, 7.69, 7.51 and
Scheme 1. Synthesis of C2-bridged ligand precursors.
Fig. 4. Ligand precursors 16/16*–21/21*.

4
H.G. Alt, M. Jung / Journal of Organometallic Chemistry 580 (1999) 1–16
Table 2
NMR data of compounds 4/4*–9/9* (250.13 MHz (1H), 69.2 MHz (13C))
1H-NMRa)
13C-NMRa)
7.83–7.79 (m, 2H), 7.67 (m, 1H), 7.55 (m, 1H),
147.6, 147.1, 140.9, 140.8 (Cq), 138.3
(ꢀCH), 127.1, 127.0, 127.0, 126.8, 125.1,
124.3, 120.0, 119.8 (CH), 114.7 (ꢀCH2),
7.45–7.35 (4H)b), 5.83 (m, 1H, ꢀCH), 5.07 (m, 1H, ꢀCH2)
5.07 (m, 1H, ꢀCH2), 4.23 (m, 1H, CH), 3.95 (m, 1H, CH),
2.31–2.10 (m, 4H, CH2), 1.93–1.83 (m, 1H, CH),
1.63–1.58 (m, 2H, CH2)
69.2
(CHOH), 44.5 (CHFlu), 41.2, 37.2,
29.9 (CH2)
7.83–7.79 (m, 2H),7.67 (m, 1H), 7.53 (m, 1H),
7.40–7.30 (4H)b), 5.83 (m, 1H, ꢀCH), 5.07 (m, 1H, CH2),
5.07 (m, 1H, ꢀCH2), 4.23 (m, 1H, CH), 3.96 (m, 1H, CH),
2.31–2.10 (m, 2H, CH2), 2.07–1.97 (m, 2H,CH2), 1.93–1.83
(m, 1H, CH), 1.63–1.58 (6H)b)
147.6, 147.1, 140.9, 140 8 (Cq), 138.3
(ꢀCH), 127.1, 127.0, 127.0, 126.8, 125.1,
124.3, 120.0, 119.8 (CH), 114.7 (ꢀCH2),
69.2 (CHOH), 44.5 (CHFlu), 41.0, 37.9,
33.5, 28.1 (CH2)c)
7.76
(d,
3J(1H,
1H)
5.6
Hz,
2H),
7.62
147.4, 147.0, 140.9, 140 7 (Cq), 139.0
(d, 3J(1H, 1H)7.0 Hz, 1H), 7.50–7.47 (d, 3J(1H, 1H)
7.0 Hz, 1H), 7.37–7.30 (4H)b), 5.80 (m, 1H, ꢀCH), 4.97
(m, 1H, ꢀCH2), 4.97 (m, 1H, ꢀCH2), 4.18 (m, 1H, CH), 3.75
(m. 1H, CH), 2.23 (m, 1H), 1.99 (m, 2H), 1.88 (m, 1H),
1.45–1.25 (12H)b)
(ꢀCH), 127.1, 127.0. 127.0, 126.8, 125.0,
124.2, 120.0, 119.8 (CH), 114.1 (ꢀCH2),
69.7 (CHOH), 44.6 (CHFlu), 41.0, 38.2,
33.7, 29.4, 28.9, 28.7, 25.4 (CH2)
7.78–7.75 (m, 2H), 7.67 (m, 1H), 7.48 (m, 1H),
7.38–7.28 (4H)b), 5.72 (m, 1H, ꢀCH), 4.94 (m, 1H, ꢀCH2),
4.94 (m, 1H, ꢀCH2), 4.89 (m, 1H, CH), 4.11 (m, 1H, CH),
2.74 (s, 3H, CH3), 2.64–2.55(m, 2H, CH2), 2.20–2.08
(m, 2H, CH2), 1.79–1.71 (m, 2H, CH2)
146.1, 146.0, 140.9, 140 7 (Cq), 136.7
(ꢀCH), 127.4, 127.3, 127.1, 126.9, 126.8,
124.9, 124.7, 119.9 (CH), 115.5 (ꢀCH2),
80.8 (CHOR), 43.9 (CHFlu), 38.3 (CH3),
37.6, 34.5, 29.8 (CH2)
7.78–7.33 (8H)b), 5.76 (m, 1H, ꢀCH), 4.97 (m, 1H, CH2),
4.97 (m, 1H, CH2), 4.83 (m, 1H, CH), 4.10 (m, 1H, CH),
2.70(s, 3H, CH3), 2.58–2.48 (m, 2H, CH2), 2.15–1.98
(m, 2H, CH2), 1.64–1.47 (m, 2H, CH2), 1.38–1.29
(4H, CH2)b)
146.4, 146.1, 139.9, 139 7 (Cq), 138.2
(ꢀCH), 127.24, 127.22, 127.18, 127.15,
124.7, 124.6, 123.9, 119.8 (CH), 114.4
(ꢀCH2), 81.3 (CHOR), 43.8 (CHFlu), 38.1
(CH3), 37.3, 35.0, 32.1, 28.1 (CH2)
7.77–7.66 (m, 2H), 7.49–7.30 (6H)b), 5.78 (m, 1H, ꢀCH),
146.2, 146.1, 140.9, 140.8 (Cq), 138.9
(ꢀCH), 127.4, 127.3, 127.1, 124.9, 124.1,
120.0 (CH)c), 114.2 (ꢀCH2), 81.6(CHOR),
44.0 (CHFlu), 38.3 (CH3), 37.6, 35.4, 33.6,
29.0, 28.7, 28.7, 24.3 (CH2)
4.98
(m,
1H,
ꢀCH2),
4.98
(m,
1H,
ꢀCH2),
4.85 (m, 1H, CH), 4.10 (m, 1H, CH), 2.72 (s, 3H, CH3),
2.08–1.97 (m, 2H,CH2), 1.64–1.60 (m, 2H, CH2),
1.31–1.22 (m, 10H, CH2)
a)in CDCl3 (saturated solution) at 25°C; b)indicated as a shift range due to signal overlap; c) 13C-NMR signals not completely separated due to
signal overlap.

H.G. Alt, M. Jung / Journal of Organometallic Chemistry 580 (1999) 1–16
5
(h=40–50%) and PE-HD (h=60–80%). The bis-
(fluorenylidene) complexes 25–27/MAO produce resins
with fusion enthalpies of 13595 J g−1 indicating a
degree of crystallinity between 45 and 48%. The
ethylene bridged fluorenylidene indenylidene complexes
22/22*–24/24*/MAO (substituted in the bridge) synthe-
size polyethylenes with enthalpies of 12095 J g−1
(h=40–43%) that are comparable with those for C,
and Si bridged complexes [16].
Scheme 3. Synthesis of the metallocene dichloride complexes.
2.6. The influence of the position of ꢀ-alkenyl sub-
stituents on the polymerization properties and on the
molecular weights of the polymers
synthesized C1-bridged bis(fluorenylidene) complexes
(C13H8–CHBu–C13H8)MCl2 (M=Zr, Hf) [14], the sig-
nals of carbon 9 of the fluorenylidene moiety appear at
l=71.9 (Zr) and 72.9 ppm (Hf). In these cases, a h1
bonding mode of the fluorenylidene ligand has to be
assumed.
The fluorenylidene indenylidene complexes 22/22*–
24/24* contain one v-alkenyl substituent in the C2-
2.5. Polymerization of ethylene
All metallocene complexes, synthesized in this study,
polymerize ethylene after activation with methylalumi-
noxane (MAO) [15–18]. One remarkable characteristic
of metallocene complexes with an v-alkenyl substituent
is their ability to incorporate themselves into the grow-
ing polymer chain as a comonomer during the polymer-
ization of a-olefins. In this way, these homogeneous
metallocene catalysts become self-immobilizing. The
further formation of polyolefin is catalyzed heteroge-
neously [21,22]. The polymer chain serves as an organic
support. Table 5 lists the self-immobilizing potential of
the individual complexes.
Fig.
9 presents the molecular weights of the
polyethylenes obtained with the three different types of
C2-bridged complexes. In comparison, resins prepared
with the fluorenylidene indenylidene complexes 22/22*–
24/24*/MAO (v-alkenyl substituent in the bridge) have
lower molecular weights (270–330×103 g mol−1) than
those produced with the bis(fluorenylidene) complexes
25–27/MAO (380–430×103 g mol−1). The C2-bridged
complexes 30–35/MAO, with the substituent in posi-
tion 3 of the indenylidene ligand, produce polyethylenes
with molecular weights of 130–170×103 g mol−1
.
Since the molecular weights of the polymers are mainly
determined by the b-H-elimination rate during the cata-
lytic process it becomes obvious that the length and the
position of the substituents R can have a considerable
influence on this chain terminating step.
The melting temperatures of the polyethylenes are
between 131.7 and 140.0°C, with most melting points in
the area of 136.091.5°C (Fig. 10, Table 5). The fusion
enthalpies show remarkable differences. Polyethylenes
produced with the C2-bridged complexes 30–35/MAO
(substituents on the indenylidene ligand) have the
highest fusion enthalpies of 16095 J g−1. This corre-
sponds to a degree of crystallinity between 53 and 57%
[23] which falls between those of conventional PE-LD
Fig. 5. Overview of the synthesized metallocene dichloride complexes.

6
H.G. Alt, M. Jung / Journal of Organometallic Chemistry 580 (1999) 1–16
Table 3
NMR data of the ligand precursors 10/10*–21/21* (250.13 MHz (1H), 69.2 MHz (13C))

H.G. Alt, M. Jung / Journal of Organometallic Chemistry 580 (1999) 1–16
7
Table 3 (Continued)
bridge. Complexes 30–35 have the ꢀ-alkenyl substituent
in position 3 of the indenylidene ligand. Polymer charac-
terization results for resins made with these complexes are
displayed in Figs. 11–13. They show that the substitution
of the v-alkenyl substituent in different positions of the
complexes produces different polymers.
The polyethylenes produced with complexes 30–35/
MAO (substituents on the indenylidene ligand) possess
molecular weights that are approximately 50% lower than
the ones for polyethylenes produced with complexes
22/22*–24/24*/MAO. The higher fusion enthalpies of the
resins prepared with complexes 30–35/MAO correspond
to crystallinities of 53–57% [23]; an increase of approx-
imately 10–18%. Complexes 30–35/MAO achieve poly-
merization activities that are about ten times higher than
those of complexes 22/22*–24/24*/MAO (substituents in
the bridge). Thus, the polymerization properties, the
molecular weights and other polymer properties (e.g.
crystallinity) can be controlled or influenced by a simple
change of the position of the substituent.

8
H.G. Alt, M. Jung / Journal of Organometallic Chemistry 580 (1999) 1–16
Fig. 6. Isomers of compounds 22/22*–24/24*.
3. Experimental
3.1. NMR spectroscopy
Jeol JNM-EX 270 E, Bruker ARX 250 and Bruker
DRX 500 spectrometers were available to record the
NMR spectra. The samples were prepared under argon
and routinely measured in CDCl3 at 25°C. The chemi-
cal shifts in 1H-NMR spectra were referred to the
residual proton signal of the solvent (l=7.24 for
CHCl3), in 13C-NMR spectra to the solvent signal
(l=77.0 for CDCl3) and in 29Si-NMR spectra to the
resonance of external TMS (l=0.0).
3.2. Mass spectroscopy
Routine measurements were conducted with a Varian
MAT CH7 instrument (direct inlet system, electron
impact ionization 70 eV). GC/MS spectra were
recorded using a Varian 3700 gas chromatograph in
combination with a Varian MAT 312 mass spectrome-
ter.
Fig. 8. (a) 250.13 MHz 1H-NMR spectrum of 25 (CDCl3, 25°C);
S=CHCl3. (b). 62.9 MHz J-modulated 13C{1H}-NMR spectrum of
25 (CDCl3, 25°C). Quaternary and CH2 carbon atoms (negative
phase), CH- and CH3 carbon atoms (positive phase) are in phase;
S=CDCl3.
3.3. Gas chromatography
A Carlo Erba HRGC gas chromatograph with flame
ionization detector was used to analyze organic com-
pounds. The gas chromatograph was equipped with a
30 m long J & W fused silica column (DB1, film
thickness 0.25 mm). Helium served as carrier gas; the
flow through the column was 3.8 ml min−1, split 1:30,
septum flushing 1.3 ml min−1. The following tempera-
ture program was routinely used: 3 min at 50°C (start-
ing phase), 5 K min−1 (heating phase), 15 min at 310°C
(plateau phase). The retention time was indicated in
seconds.
3.4. General synthesis procedure for the ꢀ-alkenyl oxi-
ranes 1–3
A total of 13.75 g (79.6 mmol) m-chlorobenzoic acid
in 250 ml methylene chloride were added dropwise to a
solution of 9 g (110 mmol) 1,v-alkadiene in 200 ml
methylene chloride and the mixture was stirred over
night. The suspension was filtered and washed with 2 M
NaHCO3, 2 N KOH and water. The organic phase was
dried over sodium sulfate, the solvent evaporated in
vacuo and the residue distilled. Yields: 60–80%.
But-3-en oxirane (1): colorless liquid, b.p. 119–
121°C. Hex-5-en oxirane (2): colorless liquid, b.p. 146–
150°C. Oct-7-en oxirane (3): colorless liquid, b.p.
75–80°C (15 Torr).
Fig. 7. C2-bridged bis(fluorenylidene) complexes.

H.G. Alt, M. Jung / Journal of Organometallic Chemistry 580 (1999) 1–16
9
Table 4
NMR data of the metallocene complexes 25–35 (250.13 MHz (1H), 69.2 MHz (13C))

10
H.G. Alt, M. Jung / Journal of Organometallic Chemistry 580 (1999) 1–16
Table 4 (Continued)

H.G. Alt, M. Jung / Journal of Organometallic Chemistry 580 (1999) 1–16
11
3.5. General synthesis procedure for the
l-fluorenyl-ꢀ-alkenyl-2-ols 4/4*–6/6*
2844 s. MS: m/e 362 (M+). 8-(9-Fluorenyl)-7-(1-in-
denyl)-1-octene (11/11*): GC 3048 s. MS: m/e 390
(M+). 10-(9-Fluorenyl)-9-(1-indenyl)-1-decene (12/12*):
GC 3233 s. MS: m/e 418 (M+). 5,6-(9,9-Bisfluorenyl)-l-
hexene (13/13*): GC 3288 s. MS: m/e 412 (M+). 7,8-
(9,9-Bisfluorenyl)-l-octene (14/14*): GC 3270 s.
9,10-(9,9-Bisfluorenyl)-l-decene (15/15*): GC 3473 s,
3480 s. MS: m/e 468 (M+).
A total of 38.2 ml n-butyllithium was slowly added
to a solution of 10.2 g (61.1 mmol) fluorene in 150 ml
diethyl ether, and the mixture was stirred for 6 h at
room temperature. At −78°C, 61.1 mmol of the corre-
sponding v-alkenyl oxirane were added to the reaction
mixture. The mixture was stirred over night at room
temperature, and the solution hydrolyzed with NH4Cl/
H2O and washed. The organic phase was evaporated in
vacuo. The conversion was quantitative. The crude
product was used without further processing for subse-
quent reactions.
3.8. General synthesis procedure for the C2-bridged
ligand precursors of the type C13H9–C2H4–C9H6R
(R=alkenyl, benzyl) 16/16*–21/21*
At −78°C, 6.25 ml n-butyllithium (1.6 M solution in
hexane) were added dropwise to a solution of 10 mmol
1-allyl-indene, 1-(3-butenyl)indene, 1-(4-pentenyl)indene,
1-(5-hexenyl)indene, 1-benzylindene or 1-(5-hexenyl-
dimethylsilyl)indene [9] in 60 ml diethyl ether and 6 ml
HMPT. The mixture was stirred for 5 h at room
temperature. At −78°C, 2.73 g (10 mmol) 1-bromo-2-
(9-fluorenyl)ethane were added to this solution and the
reaction mixture was stirred for 3 days at room temper-
ature. The mixture was hydrolyzed with 50 ml water,
the organic phase dried over sodium sulfate and the
solvent evaporated in vacuo. The residue was dissolved
in pentane and the solution filtered over silica. After the
solvent was evaporated, an oil remained that was used
without further processing for the synthesis of the
complexes. The yields were 65–75%.
1-(9-Fluorenyl)-2-[1-(3-allyl)indenyl]ethane (16/16*):
GC 2820 s. MS: m/e 348 (M+). 1-(9-Fluorenyl)-2-[1-(3-
but-3-enyl)indenyl]ethane (17/17*): GC 2976 s. MS:
m/e 362 (M+). 1-(9-Fluorenyl)-2-[1-(3-pent-4-enyl)in-
denyl]ethane (18/18*): GC 3061 s. MS: m/e 376 (M+).
1-(9-Fluorenyl)-2-[1-(3-hex-5-enyl)indenyl]ethane (19/
19*): GC 3300 s. MS: m/e 390 (M+). 1-(9-Fluorenyl)-2-
1-Fluorenyl-hex-5-en-2-ol (4/4*): GC 2200 s. MS:
m/e 264 (M+). 1-Fluorenyl-oct-7-en-2-ol (5/5*): GC
2420 s. 1-Fluorenyl-dec-9-en-2-ol (6/6*): GC 2635 s.
MS: m/e 320 (M+).
3.6. General synthesis procedure for the
1-fluorenyl-ꢀ-alkenyl-2-mesylates
(1-fluorenyl-ꢀ-alkenyl-2-methane sulfonates)
7/7*–9/9*
At −40 to −50°C, over a period of 15 min, 7.56 g
(66 mmol) mesyl chloride were added dropwise to a
solution of 61.0 mmol of the corresponding 1-fluorenyl-
v-alkenyl-2-ol and 13.91 ml (100 mmol) trimethyl-
amine in 100 ml methylene chloride. The reaction mix-
ture was stirred without further cooling for 15 min,
then extracted with ice water, cold 10% hydrochloric
acid and cold saturated sodium bicarbonate solution.
The organic phase was dried over sodium sulfate and
the solvent evaporated in vacuo to obtain the corres-
ponding 1-fluorenyl-v-alkenyl-2-mesylate.
1-Fluorenyl-hex-5-en-2-mesylate (7/7*): MS: m/e 342
(M+). 1-Fluorenyl-oct-7-en-2-mesylate (8/8*): MS:
m/e 370 (M+). 1-Fluorenyl-dec-9-en-2-mesylate (9/9*):
MS: m/e 398 (M+).
[1-(3-hex-5-enyldimethylsilyl)indenyl]ethane
(20/20*):
GC 3360 s. MS: m/e 448 (M+). 1-(9-Fluorenyl)-2-[1-(3-
benzyl)indenyl]ethane (21/21*): GC 3341 s. MS: m/e
398 (M+).
3.7. General synthesis procedure for the C2-bridged
ligand precursors of the type C13H9–CH2CHR–C9H7
and of the type C13H9–CH2CHR–C13H9 (R=alkenyl)
10/10*–15/15*
3.9. General synthesis procedure for the bridged
metallocene complexes 22/22*–35
A total of 1.0 g of the corresponding ligand precursor
was dissolved in 40 ml diethyl ether and stirred with
two equivalents n-butyllithium (1.6 M in hexane) for at
least 8 h at room temperature. Then one equivalent
zirconium tetrachloride or hafnium tetrachloride was
added and the mixture was stirred over night. The
processing was conducted according to the solubility of
the product: for ether soluble complexes, the mixture
was filtered directly from the produced lithium chloride.
For less soluble complexes, either the solvent was evap-
orated and the residue extracted with methylene chlo-
ride, or the complex was filtered over sodium sulfate,
At −78°C, 61 mmol indenyllithium or 61 mmol
fluorenyllithium in 100 ml diethyl ether were mixed
with the corresponding 1-fluorenyl-v-alkenyl-2-ol-
mesitylate, stirred for at least 4 days, hydrolyzed with
50 ml water, the organic phase dried over sodium
sulfate and the solvent evaporated in vacuo. The
residue was dissolved in pentane and the solution
filtered over silica. After crystallization in pentane at
−18°C (after 2–3 weeks), the yields were 40–50%.
6-(9-Fluorenyl)-5-(1-indenyl)-1-hexene (10/10*): GC

12
H.G. Alt, M. Jung / Journal of Organometallic Chemistry 580 (1999) 1–16
Table 5
Overview of the polymerization experiments and the polymer analysis

H.G. Alt, M. Jung / Journal of Organometallic Chemistry 580 (1999) 1–16
13
Table 5 (Continued)
a) [Zr]: [A1]=1:17000; b) i,max=maximum inside temperature of the polymerization reactor; c) the values of the second heating course of the DSC
T
were indicated as fusion enthalpies DHm; see [20]; e) the maximum of the melting peak of the second heating course of the DSC was selected as
melting point; f) Ability for copolymerization; ability of the catalyst to copolymerize in the polymer chain: ++=very good +=good,
0=sufficient,-=none; g) Polymerization time 30 min h) Polymerization time 10 min; i) Polymerization time 15 min.

14
H.G. Alt, M. Jung / Journal of Organometallic Chemistry 580 (1999) 1–16
Fig. 9. Mean intrinsic viscosity of the polyethylenes synthesized with the complex types (C13H8–CH2CHR–C9H6)ZrCl2/MAO, (C13H8–
CH2CHR–C13H8)ZrCl2/MAO and (C13H8–C2H4–C9H5R) ZrCl2/MAO (R=alkenyl, benzyl). a Cn=:v-Alkenyl substituent of the chain length n.
and the product extracted with methylene chloride or
toluene from the frit. Then the solvent was evaporated
in vacuo. The yields were 30–40%.
C31H24ZrCl2 ·0.5CH2Cl2. Calculated: C, 62.94; H, 4.19;
MS: m/e 558 (M+).
6-h5-(9-Fluorenylidene)-5-h5-(1-indenylidene)-1-hex-
ene zirconium dichloride (22/22*): orange crystals. MS:
m/e 522 (M+). 8-h5-(9-Fluorenylidene)-7-h5-(1-indeny-
lidene)-1-octene zirconium dichloride (23/23*): orange-
crystals. MS: m/e 550 (M+). 10-h5-(9-Fluorenylidene)-
9-h5-(1-indenylidene)-1-decene zirconium dichloride
(24/24*): orange crystals. MS: m/e 578 (M+). 5,6-
h5,h5-(9,9-Bisfluorenylidene)-1-hexene zirconium di-
chloride (25): red crystals. MS: m/e 572 (M+). 7,8-
h5,h5-(9,9-Bisfluorenylidene)-1-octene zirconium dichlo-
ride (26): red crystals. MS: m/e 600 (M+).
9,10-h5,h5-(9,9-Bisfluorenylidene)-1-decene zirconium
dichloride (27): red crystals. MS: m/e 628 (M+). 5,6-
h5,h5-(9,9-Bisfluorenylidene)-1-hexene hafnium dichlo-
ride (28): orange crystals. MS: m/e 660 (M+).
7,8-h5,h5-(9,9-Bisfluorenylidene)-1-octene hafnium di-
chloride (29): orange crystals. MS: m/e 688 (M+).
1-h5 -(9-Fluorenylidene)-2-h5 -[1-(3-allyl)indenylidene]
ethane zirconium dichloride (30): orange crystals. MS:
m/e 506 (M+). 1-h5-(9-Fluorenylidene)-2-h5-[1-(3-but-
3-enyl)indenylidene]ethane zirconium dichloride (31):
orange crystals. MS: m/e 522 (M+). 1-h5-(9-Fluorenyli-
dene)-2-h5-[1-(3-pent-4-enyl)indenylidene]ethane zirco-
nium dichloride (32): orange crystals. MS: m/e 536
(M+). 1-h5-(9-Fluorenylidene)-2-h5-[1-(3-hex-5-enyl)in-
denylidene]ethane zirconium dichloride (33): orange
crystals. MS: m/e 550 (M+). 1-h5-(9-Fluorenylidene)-2-
h5 - [1 - (3 - hex - 5 - enyldimethylsilyl)indenylidene]ethane
zirconium dichloride (34): orange crystals. MS: m/e
608 (M+). 1-h5-(9-Fluorenylidene)-2-h5-[1-(3-benzyl)in-
denylidene]ethane zirconium dichloride (35): orange
crystals, elemental analysis found: C, 63.71; H, 4.37;
3.10. Self-immobilization
Self-immobilization studies were conducted in
Schlenk tubes. Approximately 10 mg of the respective
complex were activated with 10 ml MAO (30% solution
in toluene), diluted with 40 ml toluene and then an
ethylene pressure of 0.4–0.6 bar was applied. The inser-
tion of the complex into the polymer chain was indi-
cated by the characteristic color of the produced
precipitate.
3.11. Polymerization reactions
3.11.1. Acti6ation of the catalyst precursors
The respective metallocene complex was weighed un-
der inert gas (approximately 8–1290.1 mg) and acti-
vated with MAO (usually 1 ml MAO (30% in toluene)
per mg metallocene dichloride complex). The solution
was diluted with toluene to an extent that approxi-
mately 0.2–0.5 mg metallocene complex were dissolved
in 1 ml toluene. Approximately 1 mg catalyst of this
solution was used for polymerization. These solutions
were used for polymerization within 60 min.
3.11.2. Polymerization of ethylene
A 1 l Bu¨chi laboratory autoclave BEP 280 was filled
with 500 ml pentane, 7 ml MAO (30% in toluene) and
the corresponding amount of catalyst solution
([Zr]:[Al]=1:17 000). The reactor was heated to 60°C
and a constant ethylene pressure of 10 bar was applied.
The polymerization was terminated after 1 h by releas-
ing the ethylene.

H.G. Alt, M. Jung / Journal of Organometallic Chemistry 580 (1999) 1–16
15
Fig. 10. Melting temperatures Tm and fusion enthalpies DHm a for polyethylenes synthesized with the complex types (C13H8–CH2CHR–
C9H6)ZrCl2/MAO, (C13H8–CH2XHR–C13H8)ZrCl2/MAO and (C13H8–C2H4–C9H5R)ZrCl2/MAO (R=alkenyl, benzyl). a The values are re-
ferred to the second heating course of the DSC; b Cn=: v-alkenyl substituent with the chain length n.
3.12. Characterization of the polymers
from 50 to 200°C, cooling phase (−20 K min−1) to
50°C; 2nd heating phase (20 K min−1) from 50 to
200°C, cooling phase (−20 K min−1) to 50°C. The
temperature was linearly corrected relative to indium
(m.p. 156.6°C). The fusion enthalpy of indium (DHm=
28.45 J g−1) was used for calibration. To determine the
crystallinity degree h, the relationship h=DHm/DHm0
was selected. DHm derives from the data of the second
heating course of the DSC. The fusion enthalpy, 290 J
g−1 [23], was assumed for DH0m for 100% crystalline
polyethylene.
3.12.1. Differential scanning calorimetry
A Perkin–Elmer DSC-7 calorimeter was available to
measure the thermal properties of the polymer samples.
Prior to the measurements, the polymer samples were
dried in vacuo. To determine the fusion enthalpies, 3–5
mg each of the polymer were fused into standard
aluminum pans and measured using the following tem-
perature program: 1st heating phase (20 K min−1
)
Fig. 11. Influence of the v-alkenyl substituent position of the ansa-
metallocene complexes on the molecular weight of the produced
polyethylenes. a Cn=: v-alkenyl substituent with the chain length n.
Fig. 12. Influence of the v-alkenyl substituent position on the poly-
merization activities of the ansa-metallocenes complexes. a Cn=: v-
alkenyl substituents with the chain length n.

16
H.G. Alt, M. Jung / Journal of Organometallic Chemistry 580 (1999) 1–16
for their financial support and Witco company for a
donation of methylaluminoxane.
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Fig. 13. Influence of the v-alkenyl substituents positon of the ansa-
metallocene complexes on the fusion enthalpies of the synthesized
polyethylenes. a Cn=:v-alkenyl substituents with the chain length n.
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3.12.2. Viscosimetry
(
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(1995) 101.
The intrinsic viscosity Mp was determined using an
Ubbelohde precision capillary viscometer in cis/trans
decalin at 13590.1°C. Prior to the measurements, the
samples were weighed into sealable small flasks and
dissolved in an exactly measured amount of decalin at
140–150°C over a period of 3–4 h. Calibration curves
(
were available for the determination of Mp. Every
polymer sample was weighed and measured twice to
reduce the error.
[19] M.A. Schmid, H.G. Alt, W. Milius, J. Organomet. Chem. 525
(1996) 9.
[20] M.A. Schmid, H.G. Alt, W. Milius, J. Organomet. Chem. 525
(1995) 15.
[21] B. Peifer, M.B. Welch, H.G. Alt, J. Organomet. Chem. 544
(1997) 115.
Acknowledgements
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[23] G. Luft, M. Dorn, Angew. Macromol. Chem. 188 (1991) 177.
We thank Phillips Petroleum Company (Bartlesville,
OK, USA) and the Deutsche Forschungsgemeinschaft
.
.