Synthesis and characterization of unbridged metallocene dichloride complexes with two differently mono-substituted indenyl ligands and their application as catalysts for the polymerization of ethene and propene

Article abstract of DOI:10.1016/S1381-1169(01)00122-4

The synthesis of unbridged metallocene dichloride complexes of the type Ind^#Ind′ZrCl₂ (Ind^# = 2-arylalkyl-substituted indenyl, Ind′ = 1-ω-alkenyl-substituted or 2-alkyl-substituted indenyl) is described. The complexes are characterized by ¹H and ¹³C NMR spectroscopy and mass spectrometry and tested for the catalytic polymerization of ethene and propene. The polymerization results and the polymer properties indicate a considerable influence of the catalyst structure on the polymerization behavior.

Full text of DOI:10.1016/S1381-1169(01)00122-4

Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
Synthesis and characterization of unbridged metallocene
dichloride complexes with two differently mono-substituted
indenyl ligands and their application as catalysts for the
polymerization of ethene and propene
Roland Schmidt, Matthias Deppner, Helmut G. Alt∗
Laboratorium für Anorganische Chemie, Universität Bayreuth, Postfach 10 12 51, D-95440 Bayreuth, Germany
Received 31 October 2000; received in revised form 18 January 2001; accepted 22 February 2001
Dedicated to Professor Max Herberhold on the occasion of his 65th birthday.
Abstract
The synthesis of unbridged metallocene dichloride complexes of the type Ind#IndꢀZrCl2 (Ind# = 2-arylalkyl-substituted
indenyl, Indꢀ = 1-␻-alkenyl-substituted or 2-alkyl-substituted indenyl) is described. The complexes are characterized by
1H and 13C NMR spectroscopy and mass spectrometry and tested for the catalytic polymerization of ethene and propene.
The polymerization results and the polymer properties indicate a considerable influence of the catalyst structure on the
polymerization behavior. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Unbridged metallocene complexes; Catalysis; Olefin polymerization; Polymer properties
1. Introduction
In this work, new unbridged zirconocene complexes
are presented containing two differently mono-subs-
tituted indenyl ligands. They are either substituted with
an ␻-alkenyl substituent in position 1, a butyl sub-
stituent in position 1 or an alkyl substituent in position
2. The second indenyl ligand is substituted in posi-
tion 2 with an arylalkyl group. These complexes were
activated with MAO and used for the catalytic poly-
merization of ethene and propene.
Metallocene complexes with group 4 metals offer a
great potential to produce polyolefins with new prop-
erties ([1–14], and references therein). In combination
with cocatalysts like methylalumoxane (MAO)
[15–18] many of them can be applied as excellent
polymerization catalysts with high productivities.
Since the discovery that symmetrically substituted
indenyl complexes of zirconium [19–35] are able to
produce polypropenes with elastomeric properties,
there is still room [36] to develop this class of metal-
locene complexes to a further extent.
2. Results and discussion
2.1. Synthesis of indene derivatives with an
arylalkyl or alkyl substituent in position 2
∗ Corresponding author. Tel.: +49-921552555;
fax: +49-921552157.
The preparation of indene derivatives with an ary-
lalkyl or alkyl substituent in position 2 proceeds from
E-mail address: helmut.alt@uni-bayreuth.de (H.G. Alt).
1381-1169/01/$ – see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S1381-1169(01)00122-4

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R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
Fig. 1. Synthesis of indene derivatives with a substituent in position 2.
a Grignard reagent of a suitable arylalkyl bromide or
an alkyl bromide and 2-indanone [37] according to the
following reaction scheme (Fig. 1).
2.2. Synthesis of indene derivatives with an
ω-alkenyl substitutent in position 1
Fig. 3. Synthesis of substituted indenylzirconiumtrichloride
complexes.
Indene is reacted with one equivalent of n-butylli-
thium to form the corresponding lithium salt [38,39].
Then a suitable ␻-alkenyl bromide [40] is added
according to the following reaction scheme (Fig. 2).
2.4. Synthesis of the metallocene dichloride
complexes 1–25
2.3. Synthesis of substituted
indenylzirconiumtrichloride complexes
The metallocene dichloride complexes 1–25 can be
prepared from the reaction of a substituted indenyl-
zirconiumtrichloride complex and the lithium salt of
the desired ␻-alkenyl-substituted indene (Fig. 4). The
prepared complexes are listed in Fig. 5.
The preparation of mixed metallocene dichloride
complexes with two different indenyl ligands via
reacting one equivalent of zirconiumtetrachloride with
one equivalent of the corresponding alkali indenyl is
not possible. Only the bis-complexes and unreacted
ZrCl4 are formed. In order to obtain the desired com-
plexes, new methods were applied [41] consisting in
the preparation of the corresponding half-sandwich
complex as the first step (Fig. 3).
2.5. Polymerization results
2.5.1. Polymerization of ethene
The synthesized metallocene complexes 1–25 were
activated with an excess of MAO (Al:Zr = 3.000:1).
Fig. 2. Preparation of indene derivatives with a substitutent in position 1.

R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
45
Fig. 4. Synthesis of unsymmetric unbridged bis(indenyl) complexes of zirconium.
Ethene was applied into the reactor with a pressure of
10 bar. The slurry polymerization in 500 ml n-pentane
was carried out at 60◦C. The polymerization results
are shown in Table 1.
Complexes 1–16 differ in the number k of spacer
methylene groups between the indenyl and the phenyl
substituent. The other indenyl ligand is substituted
with an ␻-alkenyl group with different numbers of car-
bon atoms n. The productivities range from 40.000 to
250.000 g(PE)/g(Zr) h−1 (see Table 1). This is con-
siderably less than the activity of the unsubstituted
bis(indenyl) complex (Ind)2ZrCl2 (3.200.000 g(PE)/
Fig. 5. Synthesized mixed unbridged complexes 1–25.

46
R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
Table 1
Polymerization results of homogeneous ethene polymerization with complexes 1–25/MAO a
¯
Catalyst precursor
Productivity
(g(PE)/g(Zr) h−1
Mn (g/mol)
Polydispersity
¯
¯
)
[Mw/Mn]
118.200
223.700
4.76
70.000
172.000
5.14
193.100
59.400
40.000
279.900
249.200
45.400
3.73
3.27
10.12

R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
47
Table 1 (Continued )
¯
Catalyst precursor
Productivity
(g(PE)/g(Zr) h−1
Mn (g/mol)
Polydispersity
¯
¯
)
[Mw/Mn]
151.000
246.200
4.55
198.300
144.500
5.78
191.000
119.100
7.41
123.900
179.900
5.83
200.800
256.900
4.22

48
R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
Table 1 (Continued )
¯
Catalyst precursor
Productivity
(g(PE)/g(Zr) h−1
Mn (g/mol)
Polydispersity
¯
¯
)
[Mw/Mn]
249.400
151.000
150.600
124.000
8.64
239.500
4.13
121.300
9.23
112.000
150.300
6.80
156.300
319.300
3.94

R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
49
Table 1 (Continued )
¯
Catalyst precursor
Productivity
(g(PE)/g(Zr) h−1
Mn (g/mol)
Polydispersity
¯
¯
)
[Mw/Mn]
180.100
124.500
9.12
40.200
141.100
3.70
19.86
4.98
89.600
47.800
136.800
339.800
85.400
41.300
23.33
115.900
200.000
6.01

50
R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
Table 1 (Continued )
¯
Catalyst precursor
Productivity
(g(PE)/g(Zr) h−1
Mn (g/mol)
Polydispersity
¯
¯
)
[Mw/Mn]
115.400
223.000
5.27
75.800
44.800
2.76
105.400
175.300
5.50
176.000
112.300
5.94
a Polymerization parameters: polymerization in n-pentane; at 60◦C; 60 min; Al:Zr ratio = 3.000:1.
g(Zr) h−1) [42]. One reason for this behavior could be
the negative steric effect of indenyl substituents on the
growth of the polymer chain during the polymerization
process.
productivity. An additional change of this substituent
from position 1 to position 2 of the indenyl ligand
causes a further loss of activity.
The molecular weights (Table 1) of the produced
polyethylenes do not indicate a uniform trend. In most
cases, they are slightly lower than the molecular
weight of the polyethylene obtained with (Ind)2ZrCl2/
Independent from the number k of CH2-spacer
groups (Fig. 4), the highest productivities (200.000–
250.000 g(PE)/g(Zr) h−1) were found for complexes
with an ␻-pentenyl group (3: k = 0; 7: k = 1; 11:
k = 2; 15: k = 3).
¯
MAO under identical reaction conditions Mn
=
470.000 g/mol. It is surprising that the molecular
¯
The influence of structural ligand parameters on the
productivity becomes obvious in complexes 10, 25 and
22 (Fig. 6) when the change from an ␻-alkenyl group
in position 1 of the indenyl ligand to an alkyl group
of the same number of carbon atoms triggers a loss in
mass number averages (Mn) of polyethenes produced
with complexes 18 and 20 (even number of carbon
atoms in the alkyl group) are reduced drastically in
comparison to complexes 17 and 19 with an odd
number of carbon atoms (Fig. 7). The polydispersities

R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
51
Fig. 6. Influence of different substitution patterns at the indenyl ligand on polyethene productivity.
ranges from 3.7 to 10. Normally, single site metal-
locene catalysts produce lower polydispersities (≈2).
We explain our results with the formation of multi-site
catalysts that are generated by the rotation of the
substituted ␲-ligands.
classical complex of Coates and Waymouth [19] by a
factor of 3.5 (Fig. 8).
A reduction of the productivity can be observed
when the alkyl substituent changes its position from
2 to 1 at the indenyl ligand (25). The substitution of
this alkyl group with an ␻-alkenyl group (complex 10)
reduces the productivity by 90% (Fig. 9).
2.5.2. Polymerization of propene
¯
The polymerization of propene was conducted as a
bulk polymerization in 500 ml liquid propene at 0◦C
(all data in Table 2).
The molecular weights Mn of the polypropenes
produced with complexes 17–24 ranges from 60.000
to 95.000 g/mol. An exception are the data of those
polypropenes produced with complexes 19 and
Complexes 17–24 of the type Ind#IndꢀZrCl2 (Ind#
= 2-arylalkyl-substituted indenyl, Indꢀ = 2-alkyl-
substituted indenyl) show productivities up to 64.000
g(PP)/g(Zr) h−1. Complex 22 exceeds the producti-
vity of bis(2-phenylindenyl)zirconiumdichloride, the
¯
20 which show a much higher Mn (275.000 and
189.000 g/mol). Obviously, the longer alkyl chains
(five or six carbon atoms per chain) are responsible
for this effect because they block the ␤–H-elimination
¯
Fig. 7. Change of the Mn of polyethenes produced with complexes 17–20.

52
R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
Table 2
Polymerization results of propene polymerizationa
Productivity (g(PP)/g(Zr) h−1
)
Polydispersity [Mw/Mn]
¯
Mn (g/mol)
¯
¯
Catalyst precursor
1.600
1.400
2.500
83.200
27.38
72.600
34.16 (bimodal)
105.100
2.67
3.100
90.700
3.1
2.900
81.200
8.2

R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
53
Table 2 (Continued)
Productivity (g(PP)/g(Zr) h−1
)
Polydispersity [Mw/Mn]
¯
Mn (g/mol)
¯
¯
Catalyst precursor
5.000
71.200
2.49
8.000
142.500
4.61
6.400
61.800
2.24
4.800
88.500
5.4
1.200
59.500
8.98 (bimodal)

54
R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
Table 2 (Continued)
Productivity (g(PP)/g(Zr) h−1
)
Polydispersity [Mw/Mn]
¯
Mn (g/mol)
¯
¯
Catalyst precursor
3.000
96.800
73.500
194.000
20.900
3.47
3.100
3.400
2.400
4.66
4.99
10.91
4.900
51.800
9.83 (bimodal)

R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
55
Table 2 (Continued)
Productivity (g(PP)/g(Zr) h−1
)
Polydispersity [Mw/Mn]
¯
Mn (g/mol)
¯
¯
Catalyst precursor
3.700
121.500
3.87 (bimodal)
18.800
93.300
6.04
41.100
60.000
6.17
36.400
276.800
2.66
31.600
62.800
163.600
3.59
6.400
142.5 (bimodal)

56
R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
Table 2 (Continued)
Productivity (g(PP)/g(Zr) h−1
)
Polydispersity [Mw/Mn]
¯
Mn (g/mol)
¯
¯
Catalyst precursor
64.000
57.200
9.55
60.100
46.600
81.62 (bimodal)
57.400
84.700
12.92
13.000
96.700
5.56
a Polymerization parameters: bulk polymerization in 500 ml liquid propene at 0◦C; Al:Zr ratio = 3.000:1.
process as terminating step during the polymeriza-
tion. Polydispersities are between 2.6 and 13. Some
polypropenes show a bimodal polymer weight dis-
tribution (21 and 23) (see Fig. 10) and much higher
polydispersities. The explanation for this effect
could be a change of the nature of the active sites
in the polymerization process as a consequence of
intramolecular ligand rotation.
This behavior is only observed at polypropenes that
were produced with a catalyst with a –C2H4-spacer
group between the indenyl and the phenyl ring and
additionally an alkyl side chain with an odd number of
carbon atoms at the second indenyl ligand. The change
from position 2 to 1 of the alkyl group (25) has no
influence on the polymer properties (Table 3).
The produced polypropenes are supposed to con-
sist of atactic and isotactic blocks [19]. The tacticities
were measured. The pentad distribution was deter-
mined with established methods [45–48]. The aver-
age isotacticity of all polypropenes is about 15 % as
confirmed by 13C NMR spectroscopy (see Fig. 11).
However, it is not clear at this point whether the
polypropenes produced by the asymmetric catalysts
consist of only one sort of alternating isotactic or at-
actic blocks or not. According to Fig. 12, there should
exist two different rac isomers to produce two different

R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
57
Fig. 8. Polypropene productivity dependence on the molecular structure of the metallocene complex.
isotactic polypropene blocks and two different meso
3. Experimental
isomers to produce two different atactic polypropene
blocks.
All preparations were performed under inert gas
atmosphere using standard Schlenk technique in
order to avoid air and moisture. As inert gas purified
and dried argon was used (BTS catalyst, molecu-
lar sieves). All solvents were purchased in technical
grade and purified by distillation over Na/K alloy. All
other chemicals were commercially available or were
synthesized according to literature procedures.
Different from ansa-metallocene complexes with
␻-alkenyl substituents the unbridged metallocene
complexes 1–16 do not undergo self-immobilization
[43,44]. The rotation of the aromatic ligand around
the indenyl-metal-bond axis could be so fast that the
olefin function of the substituent hardly has no chance
to copolymerize.
Fig. 9. Influence of structural parameters of the complexes on polypropene productivities.

58
R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
Fig. 10. HT-GPC of the polypropenes produced with complex 23. Bulk polymerization (500 ml propene) at 0◦C; Al:Zr = 3.000:1.
NMR spectra were recorded in CDCl3 at 25◦C on
boiling 1,2,4-trichlorobenzene. Measurements were
performed at 150◦C. The HT-GPC was calibrated
with polystyrene standards.
a Bruker ARX 250 instrument. The chemical shifts in
1
the H NMR spectra were referenced to the residual
proton signal of the solvent (δ = 7.24 ppm for CHCl3);
the carbon resonances in 13C NMR spectra were also
referenced to the solvent signal (δ = 77.0 ppm for
CDCl3).
3.1. General procedure for the synthesis of
2-arylalkyl-substituted indene derivatives
Mass spectra were recorded on a Varian MAT CH7
instrument (direct inlet system, electron impact ion-
ization 70 eV).
To a suspension of 3.37 g (139.0 mmol) magne-
sium chips in 150 ml of diethylether 14.0 mmol of a
suitable alkylaryl bromide were added. After 10 min
125.0 mmol of the alkylaryl bromide dissolved in
100 ml of diethylether were added dropwise fol-
lowed by a stirring period of about 2 h. Then 16.5 g
2-indanone, dissolved in 150 ml diethylether, were
slowly added. The stirring was continued over night.
Then the mixture was hydrolyzed with a 5 mol HCl
solution at 0◦C. The organic layer was washed twice
with a NaHCO3 solution and dried over Na2SO4. The
solvent was removed. The yields of the corresponding
alcoholic compounds were between 75 and 90%.
The alcoholic compound was dissolved in 250 ml
toluene and 10.0 mmol of p-toluene sulfonic acid were
added. The mixture was refluxed until the formed
water had separated in a Dean–Stark apparatus. After
cooling to room temperature, the mixture was washed
with a NaHCO3 solution. The organic layer was dried
over Na2SO4 and the solvent was removed in vacuo.
Polymerizations were conducted in a 1 l Büchi steel
reactor equipped with a mechanical stirrer. Ethene was
polymerized at 60◦C and 10 bar ethene pressure for
1 h in n-pentane. Propene was polymerized in bulk
at 0◦C. MAO was used as a 30% solution in toluene
from Witco, Germany. The Al:Zr ratio was 3000:1.
The polymerization reactions were stopped by venting
excess ethene and propene. The obtained polymer was
washed with HCl/methanol and dried in vacuo.
Polymer data were recorded on a Waters HT-GPC
150C instrument. For the separation four successively
connected polystyrene columns were used. The pore
diameters of the single columns were 500, 1.000,
10.000 and 100.000 Å. For the refractometric detec-
tion, a refractometer RI Waters 401 was used with de-
gassed 1,2,4-trichlorobenzene (flow rate of 1 ml/min)
as a solvent. Polymer samples were dissolved in

R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
59
Table 3
NMR data of complexes 1–25
Complex
1H NMRa
13C NMRb
7.73–7.60 (m, 3H), 7.54–7.24 (m, 8H),
6.84–6.79 (m, 2H), 6.48 (m, 1H), 6.15
(m, 1H), 6.03–5.88 (m, 1H), 5.98 (m,
1H), 5.75 (m, 1H), 5.20–5.05 (m, 2H),
3.82–3.65 (m, 2H)
(Cq): 146.4, 143.2, 133.9, 133.3, 127.8, 127.1, 122.0
(CH): 135.9, 128.9, 128.1, 126.3, 126.2, 125.6, 125.5,
125.2, 123.7, 122.1, 120.4, 103.2, 100.0, 99.1
(CH2): 116.6, 32.3
7.74–7.60 (m, 3H), 7.52–7.22 (m, 8H),
6.81–6.77 (m, 2H), 6.09 (d, 3J(1H, 1H)
3.1 Hz, 1H), 6.03 (d, 3J(1H, 1H)
3.1 Hz, 1H), 6.00–5.78 (m, 2H), 5.62
(m, 1H), 5.02–4.94 (m, 2H), 3.56–3.50
(m, 2H), 2.98–2.76 (m, 2H)
(Cq): 144.9, 142.5, 135.8, 133.2, 132.3, 124.9, 121.8
(CH): 137.3, 128.5, 128.3, 127.5, 126.3, 126.2, 126.1,
125.2, 124.3, 120.6, 103.2, 99.7, 99.5
(CH2): 114.8, 38.6, 33.6
7.74–7.54 (m, 3H), 7.52–7.22 (m, 8H),
6.81–6.77 (m, 2H), 6.10 (d, 3J(1H, 1H)
3.2 Hz, 1H), 6.01 (d, 3J(1H, 1H)
3.2 Hz, 1H), 5.97–5.74 (m, 1H), 5.84
(d, 3J(1H, 1H) 3.2 Hz, 1H), 5.61 (d,
3J(1H, 1H) 3.1 Hz, 1H), 5.09–4.94 (m,
2H), 3.51 (m, 2H), 3.01–2.90 (m, 2H),
2.82–2.70 (m, 2H)
(Cq): 133.4, 133.0, 127.2, 126.2, 124.4
(CH): 138.2, 128.9, 128.7, 127.5, 126.7, 126.5, 125.7,
125.5, 125.4, 120.2, 103.2, 99.9, 99.0
(CH2):114.7, 33.3, 29.0, 27.4
7.74–7.53 (m, 3H), 7.52–7.20 (m, 8H),
6.83–6.79 (m, 2H), 6.09 (d, 3J(1H, 1H)
3.2 Hz, 1H), 6.01 (d, 3J(1H, 1H)
(Cq): 133.6, 133.3, 127.5, 126.9, 126.4, 124.8
3.2 Hz, 1H), 5.88–5.75 (m, 1H), 5.84
(d, 3J(1H, 1H) 3.2 Hz, 1H), 5.63 (d,
3J(1H, 1H) 3.1 Hz, 1H), 5.06–4.95 (m,
2H), 3.37 (m, 2H), 3.02–2.74 (m, 2H),
2.73–2.58 (m, 2H), 2.15–2.05 (m, 2H)
(CH): 138.7, 128.9, 128.7, 128.5, 127.7, 127.2, 126.7,
126.2, 125.2, 120.8, 119.1, 118.9, 103.3, 99.9, 99.3
(CH2): 114.5, 39.0, 33.5, 29.5, 28.7
7.71–7.58 (m, 3H), 7.44–7.38 (m, 1H),
7.33–7.20 (m, 7H), 7.15–7.11 (m, 2H),
6.29 (d, 1H), 6.11 (d, 1H), 5.94–5.87
(m, 2H), 5.22 (d, 3J(1H, 1H) 3.1 Hz,
1H), 5.12–5.04 (m, 2H), 3.95–3.89 (m,
2H), 3.74–3.58 (m, 2H)
(Cq): 141.8, 139.8, 127.3, 126.3, 125.3, 122.2
(CH): 135.7, 128.8, 128.5, 126.7, 126.4, 125.7, 125.6,
125.5, 125.4, 123.6, 119.3, 104.6, 104.0, 99.9
(CH2): 116.6, 37.8, 32.4

60
R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
Table 3 (Continued)
Complex
1H NMRa
13C NMRb
7.74–7.62 (m, 3H), 7.51–7.47 (m, 1H),
7.34–7.22 (m, 7H), 7.16–7.13 (m, 2H),
6.31 (d, 1H), 6.07 (d, 1H), 5.93–5.86 (m,
2H), 5.29 (d, 3J(1H, 1H) 3.1 Hz, 1H),
5.09–5.00 (m, 2H), 3.94–3.87 (m, 2H),
3.11–3.04 (m, 2H), 2.90–2.80 (m, 2H)
(Cq): 141.3, 139.4, 127.5, 126.9, 124.8, 123.5,
(CH): 137.3, 128.4, 128.1, 126.1, 125.9, 125.2, 125.1,
125.0, 124.9, 123.1, 119.0, 104.1, 103.8, 99.4
(CH2): 115.0, 37.4, 33.6, 27.2
7.73–7.64 (m, 3H), 7.52–7.48 (m, 1H),
7.35–7.24 (m, 7H), 7.18–7.15 (m, 2H),
6.31 (d, 1H), 6.08 (d, 1H), 5.93–5.82
(m, 2H), 5.30 (d, 3J(1H, 1H) 3.1 Hz,
1H), 5.12–5.03 (m, 2H), 3.97–3.87 (m,
2H), 3.03–2.97 (m, 2H), 2.78–2.72 (m,
2H), 2.18–2.10 (m, 2H)
(Cq): 141.7, 139.8, 128.1, 127.3, 126.2, 125.2, 124.8
(CH): 138.3, 128.8, 128.5, 126.6, 126.5, 125.7, 125.6,
125.5, 125.4, 123.8, 119.3, 104.5, 104.2, 99.8
(CH2): 115.0, 37.8, 33.5, 29.2, 27.6
7.72–7.62 (m, 3H), 7.51–7.46 (m, 1H),
7.35–7.19 (m, 7H), 7.17–7.14 (m, 2H),
6.31 (d, 3J(1H, 1H) 2.2 Hz, 1H), 6.09
(d, 3J(1H, 1H) 2.2 Hz, 1H), 5.90–5.83
(m, 2H), 5.28 (d, 3J(1H, 1H) 3.1 Hz,
1H), 5.09–4.99 (m, 2H), 3.97–3.86 (m,
2H), 3.03–2.98 (m, 2H), 2.77–2.72 (m,
2H), 2.17–2.09 (m, 4H)
(Cq): 141.7, 141.3, 128.1, 127.2, 126.2, 125.2, 125.0
(CH): 138.7, 128.9, 128.5, 126.6, 126.4, 125.7, 125.6,
125.4, 123.7, 119.2, 104.3, 104.2, 99.8
(CH2): 114.5, 37.8, 33.6, 29.9, 28.9, 28.1
7.76–7.59 (m, 3H), 7.44–7.39 (m, 1H),
7.36–7.19 (m, 7H), 7.15–7.11 (m, 2H),
6.20 (d, 3J(1H, 1H) 2.2 Hz, 1H), 6.04
(d, 3J(1H, 1H) 2.2 Hz, 1H), 5.98–5.82
(m, 1H), 5.89 (d, 3J(1H, 1H) 3.1 Hz,
1H), 5.22 (d, 3J(1H, 1H) 3.2 Hz, 1H),
5.12–5.06 (m, 2H), 3.71–3.53 (m, 2H),
2.97–2.88 (m, 2H), 2.84–2.78 (m, 2H)
(Cq): 142.8, 141.1, 127.1, 126.0, 125.0, 122.1
(CH): 135.7, 128.5, 128.3, 126.7, 126.1, 125.6, 125.5,
125.3, 123.6, 119.3, 104.3, 103.5, 99.9
(CH2): 116.6, 36.4, 33.6, 32.4
7.70–7.22 (m, 11H), 6.95–6.89 (m, 2H),
6.10 (d, 3J(1H, 1H) 3.2 Hz, 1H), 6.04
(d, 3J(1H, 1H) 3.2 Hz, 1H), 5.88–5.70
(m, 1H), 5.63 (m, 1H), 5.12–4.94 (m,
3H), 3.83 (m, 2H), 3.05–2.89 (m, 2H),
2.87–2.66 (m, 2H), 2.55–2.25 (m, 2H)
(Cq): 145.0, 133.3, 133.1, 127.0, 125.8, 123.8, 122.4
(CH): 137.7, 128.9, 128.7, 128.2, 127.5, 126.7, 125.6,
124.7, 123.8, 121.0, 103.6, 100.1, 99.9
(CH2): 115.5, 39.0, 34.0, 27.5, 27.4

R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
61
Table 3 (Continued)
Complex
1H NMRa
13C NMRb
7.71–7.22 (m, 11H), 6.82–6.78 (m,
2H), 6.11 (d, 3J(1H, 1H) 3.2 Hz, 1H),
6.03 (d, 3J(1H, 1H) 3.2 Hz, 1H),
5.90–5.72 (m, 1H), 5.64 (d, 3J(1H, 1H)
3.2 Hz, 1H), 5.08–4.97 (m, 3H), 3.83
(m, 2H), 3.04–2.79 (m, 4H), 2.75–2.52
(m, 2H), 2.25–2.01 (m, 2H)
(Cq): 133.6, 133.3, 127.4, 127.0, 126.2, 124.5, 123.0
(CH): 138.3, 128.9, 128.7, 126.7, 126.5, 125.7, 125.3,
123.8, 121.0, 120.0, 103.5, 100.2, 99.9
(CH2): 114.9, 39.0, 33.4, 29.2, 27.5, 27.3
7.73–7.20 (m, 11H), 6.82–6.79 (m, 2H),
6.12 (d, 3J(1H, 1H) 3.2 Hz, 1H), 6.01
(d, 3J(1H, 1H) 3.1 Hz, 1H), 5.91–5.69
(m, 1H), 5.62 (d, 3J(1H, 1H) 3.1 Hz,
1H), 5.08–4.92 (m, 3H), 3.83 (m, 2H),
3.36 (m, 2H), 3.02–2.77 (m, 2H),
(Cq): 133.6, 133.3, 127.5, 127.1, 126.2, 125.0, 123.5
(CH): 138.7, 128.8, 127.5, 126.7, 126.5, 125.5, 124.9,
123.8, 120.9, 119.3, 103.5, 99.9, 99.2
(CH2): 39.0, 37.7, 33.5, 29.5, 28.7, 27.9, 27.8
2.74–2.53 (m, 2H), 2.22–2.01 (m, 4H)
7.76–7.58 (m, 3H), 7.55–7.15 (m,
10H), 6.27 (m, 1H), 6.11 (m, 1H),
6.08–5.83 (m, 2H), 5.28 (m, 1H),
5.20–5.01 (m, 2H), 3.76–3.49 (m, 2H),
3.37 (m, 2H), 2.80–2.56 (m, 4H)
(Cq): 150.3, 143.4, 142.2, 127.2, 126.1, 125.2, 122.0
(CH): 135.8, 128.5, 128.4, 126.3, 125.9, 125.8, 125.7,
123.6, 123.4, 119.9, 103.7, 99.1, 99.0
(CH2): 115.6, 41.0, 35.6, 31.3, 28.9
7.76–7.58 (m, 3H), 7.57–7.16 (m,
10H), 6.29 (m, 1H), 6.09 (m, 1H),
6.03–5.85 (m, 2H), 5.30 (m, 1H),
5.19–5.00 (m, 2H), 3.40 (m, 2H),
3.25–2.57 (m, 6H), 2.52–2.27 (m, 2H)
(Cq): 149.9, 142.8, 141.8, 127.4, 126.8, 125.8, 122.1
(CH): 137.4, 128.0, 127.9, 126.1, 125.9, 125.4, 124.9,
123.3, 119.6, 103.8, 103.5, 99.3, 98.8
(CH2): 115.0, 40.7, 35.1, 33.5, 31.8, 30.2
7.76–7.58 (m, 3H), 7.55–7.16 (m, 10H),
6.30 (m, 1H), 6.14 (m, 1H), 6.03–5.80
(m, 1H), 5.75 (m, 1H), 5.32 (m, 1H),
5.19–5.00 (m, 2H), 3.37 (m, 2H),
(Cq): 149.9, 142.8, 141.8, 141.5, 126.9, 125.8, 124.3
(CH): 137.9, 128.1, 128.0, 126.0, 125.8, 125.5, 125.0,
123.3, 119.6, 103.8, 103.5, 99.3, 98.9
3.20–2.60 (m, 6H), 2.30–2.00 (m, 4H)
(CH2): 114.5, 40.7, 35.1, 33.3, 31.5, 30.4, 28.9

62
R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
Table 3 (Continued)
Complex
1H NMRa
13C NMRb
7.76–7.57 (m, 3H), 7.55–7.14 (m, 10H),
6.25 (m, 1H), 6.09 (m, 1H), 5.88–5.77
(m, 1H), 5.73 (m, 1H), 5.32 (m, 1H),
5.07–4.96 (m, 2H), 3.36 (m, 2H),
(Cq): 150.3, 143.1, 142.3, 141.9, 128.0, 127.3, 124.7
(CH): 138.7, 128.7, 128.5, 128.3, 126.3, 125.8, 125.5,
123.4, 120.0, 104.2, 103.9, 99.6, 99.2
3.02–2.60 (m, 6H), 2.20–1.98 (m, 6H)
(CH2): 114.6, 41.1, 35.6, 33.6, 30.7, 30.6, 31.3, 28.7
7.72–7.68 (m, 4H), 7.34–7.10 (m, 7H),
7.10–7.07 (m, 2H), 5.93–5.90 (m, 4H),
3.77 (s, 2H), 2.40 (t, 3J(1H, 1H)
7.8 Hz, 2H), 1.75–1.70 (m, 2H),
1.06–1.00 (m, 3H)
(Cq): 142.7, 142.5, 140.7, 139.5, 125.7
(CH): 128.5, 128.0, 125.9, 125.0, 124.9, 124.8, 124.7,
124.6, 123.0, 119.4, 105.1, 104.9
(CH2): 37.0, 32.0, 23.5
(CH3): 13.5
7.68–7.64 (m, 4H), 7.28–7.03 (m, 7H),
7.02–6.96 (m, 2H), 5.88–5.84 (m, 4H),
3.72 (s, 2H), 2.38 (t, 3J(1H, 1H)
7.8 Hz, 2H), 1.68–1.62 (m, 2H),
(Cq): 142.9, 142.8, 140.7, 139.5, 125.9
(CH): 128.2, 128.0, 126.5, 125.0, 124.9, 124.8, 124.7,
124.6, 124.5, 123.1, 123.0, 119.4, 105.1, 105.0, 104.8
(CH2): 37.0, 32.5, 30.7, 22.1
1.34–1.25 (m, 2H), 0.98–0.93 (m, 3H)
(CH3): 13.4
7.74–7.69 (m, 4H), 7.33–7.09 (m, 7H),
7.08–7.04 (m, 2H), 5.93–5.89 (m, 4H),
3.77 (s, 2H), 2.42 (t, 3J(1H, 1H)
7.2 Hz, 2H), 1.71–1.67 (m, 2H),
(Cq): 142.9, 142.7, 140.8, 139.3, 125.7
(CH): 128.3, 128.1, 125.9, 125.2, 125.1, 125.0, 124.9,
124.8, 124.7, 123.1, 123.0, 119.4, 105.1, 105.0, 104.8
(CH2): 37.0, 31.0, 30.9, 30.0, 22.0
1.46–1.28 (m, 4H), 0.99–0.93 (m, 3H)
(CH3): 13.6
7.72–7.68 (m, 4H), 7.33–7.09 (m, 7H),
7.08–7.05 (m, 2H), 5.92–5.88 (m, 4H),
3.76 (s, 2H), 2.41 (t, 3J(1H, 1H)
7.8 Hz, 2H), 1.71–1.67 (m, 2H),
(Cq): 143.0, 142.8, 140.7, 139.5, 125.6
(CH): 128.2, 128.0, 125.9, 125.2, 125.1, 125.0, 124.9,
124.8, 124.7, 123.1, 123.0, 119.4, 105.1, 105.0, 104.8
(CH2): 37.0, 31.1, 31.0, 30.3, 28.6, 22.0
(CH3): 13.6
1.46–1.26 (m, 6H), 1.00–0.91 (m, 3H)
7.72–7.67 (m, 4H), 7.33–7.23 (m, 7H),
7.14–7.09 (m, 2H), 5.92–5.82 (m, 4H),
2.75–2.71 (m, 4H), 2.41–2.34 (m, 4H),
1.05–1.00 (m, 3H)
(Cq): 142.7, 142.5, 141.6, 140.7, 125.6
(CH): 128.0, 127.9, 125.8, 125.5, 125.0, 124.7, 123.1,
123.0, 119.4, 105.0, 104.9, 104.7
(CH2): 36.0, 32.9, 32.7, 23.6
(CH3): 13.4

R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
63
Table 3 (Continued)
Complex
1H NMRa
13C NMRb
7.72–7.67 (m, 4H), 7.33–7.23 (m, 7H),
7.14–7.09 (m, 2H), 5.89–5.79 (m, 4H),
2.72 (m, 4H), 2.43–2.37 (m, 4H),
(Cq): 142.9, 142.8, 141.6, 140.7, 125.6
(CH): 128.0, 127.9, 125.8, 125.5, 125.1, 124.7, 123.3,
123.1, 123.0, 119.4, 104.9, 104.8, 104.6
(CH2): 36.0, 32.6, 32.4, 30.7, 22.1
(CH3): 13.4
1.41–1.33 (m, 2H), 1.02–0.96 (m, 3H)
7.72–7.68 (m, 4H), 7.33–7.24 (m, 7H),
7.14–7.09 (m, 2H), 5.91–5.81 (m, 4H),
2.74–2.71 (m, 4H), 2.43–2.37 (m, 4H),
1.42–1.29 (m, 4H), 1.00–0.94 (m, 3H)
(Cq): 143.0, 142.8, 141.6, 140.7, 125.6
(CH): 128.0, 127.8, 125.6, 125.3, 125.2, 123.1, 123.0,
119.4, 104.8, 104.7, 104.6
(CH2): 36.0, 32.7, 31.1, 31.0, 30.0, 22.0
(CH3): 13.5
7.72–7.67 (m, 4H), 7.33–7.24 (m, 7H),
7.14–7.09 (m, 2H), 5.90–5.80 (m, 4H),
2.73 (m, 4H), 2.43–2.37 (m, 4H),
(Cq): 143.0, 142.8, 141.6, 140.7, 125.6
(CH): 128.0, 127.9, 125.5, 125.0, 124.7, 123.1, 123.0,
119.4, 104.9, 104.8, 104.7
1.39–1.27 (m, 6H), 1.01–0.94 (m, 3H)
(CH2): 36.0, 32.8, 31.1, 31.0, 30.3, 28.6, 22.1
(CH3): 13.7
7.74–7.13 (m, 13H), 6.23 (m, 1H), 6.02
(m, 1H), 5.87 (m, 2H), 5.28 (m, 2H),
3.01–2.81 (m, 4H), 1.60–1.34 (m, 4H),
1.06–0.98 (m, 3H)
(Cq): 142.4, 141.2, 141.0, 127.0
(CH): 128.1, 128.0, 126.1, 125.9, 125.2, 125.0, 124.0,
123.3, 121.6, 118.8, 118.6, 103.5, 99.3, 98.7
(CH2): 36.0, 33.2, 31.8, 27.5, 22.2
(CH3): 13.5
a 25◦C, in chloroform-d1, δ (ppm) rel. chloroform (7.24).
b 25◦C, in chloroform-d1, δ (ppm) rel. chloroform-d1 (77.0).
The residue was dissolved in n-pentane and filtered
over silica. After crystallization at −25 or −78◦C, the
desired indene derivatives were obtained in an overall
yield of 40–75%.
temperature for 5 h, the solution was cooled to −78◦C
and an equimolar amount of an ␻-alkenyl bromide or
butylbromide was added. The mixture was hydrolyzed
with 80 ml of water and stirred over night at room
temperature. The organic layer was separated and
dried over Na2SO4. The solvent was evaporated and
the residue was distilled in vacuo. Yield: 80–90%.
3.2. General procedure for the synthesis of
1-ω-alkenyl-substituted indene derivatives and
1-butylindene
3.3. General procedure for the synthesis of
substituted 1-(tributylstannyl)indene derivatives
To 10.0 ml (85.1 mmol) indene, dissolved in 150 ml
diethylether and 15 ml tetrahydrofuran, 53.2 ml
(85.1 mmol) n-butyllithium (1.6 M in n-hexane) were
added dropwise at −78◦C. After stirring at room
12.0 mmol of the corresponding indene deriva-
tive were dissolved in 150 ml of diethylether and

64
R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
derivative, dissolved in 80 ml of toluene, was added.
The mixture was stirred overnight. After filtration and
washing with n-pentane the solvent was evaporated
in vacuo. Yield: 70–95%.
3.5. General procedure for the synthesis of the
unbridged metallocene dichloride complexes 1–25
To a solution of 4.1 mmol of the alkyl or
␻-alkenyl-substituted indene derivative, dissolved in
150 ml of diethylether, 2.6 ml (4.1 mmol) n-butyllithium
(1.6 M in n-hexane) were added dropwise at −78◦C.
After completion of the deprotonation, the mix-
ture was cooled again to −78◦C. The desired
half-sandwich complex was added equimolarly. After
stirring overnight and evaporation of the solvent the
residue was extracted with methylenedichloride. The
suspension was filtered over Na2SO4. The filtrate was
evaporated. The precipitating complex was recrystal-
lized from toluene at −78◦C. Yield: 60–90%.
Fig. 11. Section of the 13C NMR spectrum (measured at 90◦C)
of the polypropene produced with complex 23/MAO (peak of
isotactic rate underlined (mmmm)).
an equimolar amount of n-butyllithium (1.6 M in
n-hexane) was added dropwise at −78◦C. After
stirring at room temperature for several hours and
recooling to −78◦C, tributyltinchloride was added.
Stirring was continued overnight at room tempera-
ture. The solvent was evaporated and the residue was
suspended in n-pentane. The suspension was filtered
through Na2SO4 and the filtrate was evaporated.
Yield: quantitatively.
3.6. Spectroscopic characterization
Complexes 1–25 were characterized by 1H and 13
C
NMR spectroscopy (Table 3). In addition, mass spec-
trometry confirmed the composition of the complexes.
3.4. General procedure for the synthesis of
substituted indenylzirconiumtrichloride complexes
Acknowledgements
To a suspension of 5.17 g (22.0 mmol) zirconi-
umtetrachloride in 150 ml of toluene a solution of
an equimolar amount of a 1-(tributylstannyl)indene
We thank Phillips Petroleum Company (Bartlesville,
OK, USA) for financial support and Witco Company
(Germany) for the donation of methylalumoxane.
Fig. 12. Potential catalyst isomers.

R. Schmidt et al. / Journal of Molecular Catalysis A: Chemical 172 (2001) 43–65
65
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