Asymmetric dinuclear ansa zirconocene complexes with methyl and phenyl substituted bridging silicon atoms as dual site catalysts for the polymerization of ethylene

Article abstract of DOI:10.1016/S0020-1693(02)01491-3

Sixteen asymmetric dinuclear ansa zirconocene complexes bearing cyclopentadienyl, indenyl or fluorenyl ligands and their ligand precursors have been synthesized and characterized by NMR spectroscopy. After activation with methylalumoxane (MAO), the comple

Full text of DOI:10.1016/S0020-1693(02)01491-3

Inorganica Chimica Acta 350 (2003) 1ꢀ11
/
www.elsevier.com/locate/ica
Asymmetric dinuclear ansa zirconocene complexes with methyl and
phenyl substituted bridging silicon atoms as dual site catalysts for the
polymerization of ethylene
Helmut G. Alt *, Rainer Ernst
Laboratorium fur Anorganische Chemie der Universitat Bayreuth, Lehrstuhl fur Anorganische Chemie, Postfach 10 12 51, D-95440 Bayreuth, Germany
¨ ¨ ¨
Received 21 January 2002; accepted 4 April 2002
Dedicated to Professor Pierre Braunstein
Abstract
Sixteen asymmetric dinuclear ansa zirconocene complexes bearing cyclopentadienyl, indenyl or fluorenyl ligands and their ligand
precursors have been synthesized and characterized by NMR spectroscopy. After activation with methylalumoxane (MAO), the
complexes behave like dual site catalysts and produce polyethylenes with bimodal or broad molecular weight distributions in
homogeneous and heterogeneous media.
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Ansa zirconocene complexes; Dual site catalysts; Dinuclear asymmetric complexes; Homogeneous and heterogeneous ethylene
polymerization
1. Introduction
metallocene complexes do not unify two different
catalytic centers [6ꢀ13].
In this context silylene bridged metallocene moieties
/
In the past, monomeric metallocene complexes have
proven excellent single site catalysts for the polymeriza-
appeared as attractive building blocks due to the
SiR1R2Ã
observation that Ã
/
/
bridges give better activities
18]. Surprisingly also the
tion of ethylene and propylene [1ꢀ5]. The produced
/
than Ã
/
CR1R2Ã
/
bridges [3,14ꢀ
/
polyolefins have narrow molecular weight distributions
and this can be disadvantageous for industrial proces-
sing. In order to obtain broader molecular weight
distributions, it is possible to mix various catalysts or
the corresponding polyolefins. Both approaches can
cause additional problems and costs. Therefore, it was
the intention to solve this problem with asymmetric
dinuclear metallocene complexes. They should have the
potential of dual site catalysts. Other known dinuclear
substituents R1 and R2 have a strong influence on the
activities of these catalysts and the molecular weights of
the polymers formed [3,14ꢀ18].
/
2. Results and discussion
2.1. Synthesis of the dichlorosilane and
tetrachlorodisilane precursors
* Corresponding author. Tel.: ꢁ
157.
E-mail address: helmut.alt@uni-bayreuth.de (H.G. Alt).
/
49-921-552 555; fax: ꢁ49-921-552
/
Dichlorosilanes and tetrachlorodisilanes were synthe-
sized according to Schemes 1ꢀ3:
/
0020-1693/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0020-1693(02)01491-3

2
H.G. Alt, R. Ernst / Inorganica Chimica Acta 350 (2003) 1ꢀ11
/
Scheme 1. Synthesis of v-alkenyl substituted methyldichlorosilane
derivatives by Grignard reactions.
Scheme 5. Indenyl and fluorenyl ligand precursors 19ꢀ28.
/
2.3. Preparation of the complexes
The octenyl derivative 6 was formed in a catalytic
hydrosilation reaction [14,15]:
The dinuclear ansa zirconocene complexes were
prepared according to Scheme 6 [26,27]:
Scheme 2. Synthesis of v-octenyl methyldichlorosilane (6) by hydro-
silation reaction.
Scheme 6. Synthesis of the ansa zirconocene complexes 29ꢀ34.
/
The resulting v-alkenyl substituted methyldichlorosi-
lane derivatives were treated with phenyldichlorosilane
in catalytic hydrosilation reactions.
The indenyl and fluorenyl complexes 35ꢀ
/
44 were
prepared in an analogous manner (Scheme 7):
Scheme 3. Formation of tetrachlorodisilane derivatives by hydrosila-
tion reactions [19,20].
Scheme 7. Fluorenyl and indenyl substituted ansa zirconocene com-
plexes 35ꢀ44.
/
2.2. Synthesis of the ligand precursors
The tetrachlorodisilane derivatives were treated with 4
equiv. of sodium cyclopentadienide. The ligand precur-
sors were formed by salt elimination reactions according
For comparison the following monomeric reference
complexes R1ꢀR6 were synthesized [21,25] (Scheme 8):
/
to Scheme 4 [21ꢀ25]:
/
Scheme 4. Synthesis of the ligand precursors 13ꢀ18.
/
The indenyl and fluorenyl derivatives 19ꢀ
/
28 were
prepared in the same manner (Scheme 5):
Scheme 8. Reference catalyst precursors R1ꢀR6.
/

H.G. Alt, R. Ernst / Inorganica Chimica Acta 350 (2003) 1ꢀ
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3
2.4. Polymerization results
Table 1
Polymerization data of the catalyst precursors 29ꢀ
catalyst precursors R1ꢀ
heterogeneous ethylene polymerization reactions
/
44, the reference
/
R6 and mixtures thereof in homogeneous and
The dinuclear complexes 29ꢀ
/
44 and the reference
compounds R1ꢀR6 were activated with MAO in toluene
/
Complex Activity
[g(PE)/g(Zr)h]
Mn [g molꢃ1
HI [Mw/Mn]
Activity
[g(PE)/g(Zr)h]
solution. The homogeneous catalyst solution was used
for ethylene polymerization. In a similar manner the
corresponding activated catalyst solutions were treated
with silica gel [1 g SiO2/mmol(Zr)] and then used for
heterogeneous ethylene polymerization. The polymer-
ization results are given in Table 1:
A comparison of the homogeneous and the hetero-
geneous polymerization runs shows the surprising result
that the heterogeneous catalysts in nearly all cases are
more active than the homogeneous ones (Scheme 9).
This result is contrary to earlier observations
[20,22,26,27] and could be due to the fact that the
dinuclear complexes form cationic species more effi-
ciently on the surface of silica than in homogeneous
solution. Another explanation could derive from re-
duced deactivation processes during the polymerization
and reduced intermolecular blocking of the coordina-
tion spheres of the catalysts.
]
Mn [g molꢃ1
HI [Mw/Mn]
]
(homogeneous conditions) (heterogeneous conditions)
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
R1
61 600
36 140
13.1
84 000
202 400
54.4 a
66 000
22 520
11.0
96 000
425 000
18.6
105 000
64 420
6.2
139 000
473 000
7.7
96 000
54 890
9.2
153 000
n.d.
132 000
70 210
8.8
136 000
496 000
7.7
An increase of activity can also be observed when the
cyclopentadienyl ligand is substituted with an indenyl or
fluorenyl group. The results are summarized in Scheme
9.
The chain length of the (CH2)n spacers has also
considerable influence on the activity of the homoge-
neous or heterogeneous catalysts. The best results were
117 500
98 980
9.9
163 000
37 110
12.6
91 500
177 900
8.6
172 000
143 400
5.6
128 500
231 600
3.5
176 900
167 700
4.5
obtained for nꢂ5. A 1,5-pentylidene spacer seems to
/
provide the best distance between the two catalyst
centers to optimize the activity (Scheme 10). A crucial
factor that could determine kinetics of polymerization
could be the steric requirement for the orientation of the
polymer chains during the polymerization process.
Also the molecular weight goes up when polyethylene
is produced with a heterogeneous catalyst instead of a
homogeneous (Scheme 11). This could be indicative for
a hindered b-H elimination reaction as chain terminat-
113 200
108 000
16.7 a
185 400
940
317.2
168 200
99 600
8.4
222 700
97 780
9.3
210 000
51 360
5.5
240 000
88 870
390.6 a
240 000
282 000
35.0 a
286 000
125 500
10.3
ing step [28ꢀ30].
/
241 300
496 600
3.0
370 000
363 100
5.9
190 000
775 700
2.3
227 400
800 600
2.4
252 000
224 200
44.9 a
253 000
448 400
44.6 a
256 000
841 400
118.9 a
232 000
396 400
3.3
Scheme 9. Activities of various dinuclear catalysts in homogeneous
and heterogeneous polymerization reactions of ethylene. Cp?ꢂC5H4,
Ind?ꢂC9H6, Flu?ꢂC13H3.
/
109 000
102 000
/
/

4
H.G. Alt, R. Ernst / Inorganica Chimica Acta 350 (2003) 1ꢀ
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11
Table 1 (Continued)
Complex Activity
Activity
[g(PE)/g(Zr)h]
[g(PE)/g(Zr)h]
Mn [g molꢃ1
HI [Mw/Mn]
]
Mn [g molꢃ1
HI [Mw/Mn]
]
(homogeneous conditions) (heterogeneous conditions)
95 120
2.8
104 000
2.6
R2
R3
R4
R5
R6
250 000
135 700
2.6
190 000
149 500
2.5
Scheme 10. Correlation between spacer length and activity of a
catalyst.
320 000
413 800
3.0
260 000
396 000
2.3
103 000
99 310
2.8
96 000
121 500
2.4
265 000
145 400
2.7
210 000
150 900
2.7
330 000
486 400
2.9
270 000
417 200
2.3
R1ꢁ
/
R4 101 000
69 640
3.2
97 000
104 700
3.4
Scheme 11. Molecular weights of polyethylenes from homogeneous
and heterogeneous polymerization conditions.
R2ꢁ
/
R5 241 000
195 100
4.5
193 000
184 300
8.0
R3ꢁ
/
R6 316 000
551 900
11.1
262 000
1 282 000
7.5
n.d., not determined.
a
Molecular masses were too high to be determined, curve was
extrapolated; the measured data is not involved in the discussion of the
results.
The molecular weight distributions of the produced
polyethylenes confirm the expectations: they are all of
bimodal character (Scheme 12).
Scheme 12. Polydispersities of polyethylenes from homogeneous and
heterogeneous polymerization conditions.
The broadest molecular weight distributions were
obtained with the cyclopentadienyl complexes. In these
derivatives the asymmetry of the dinuclear complex has
the strongest impact (Scheme 13).It can be postulated
that the low molecular mass fraction at a maximum
molecular weight of 100 000 g molꢃ1 is produced by the
methyl silyl catalyst moiety and the higher molecular
mass fraction (at 1 000 000 g molꢃ1) by the phenyl silyl
component. It is known from single site catalyst
experiments [22,25] that the molecular masses of those
compounds show such characteristic distributions.
In order to investigate the question whether a similar
polydispersity can be obtained by mixing the corre-
sponding monomeric complexes the following experi-
ments were conducted:
neous and heterogeneous conditions and as equimolar
mixtures.
Scheme 14 shows two single site catalyst precursors
that result from the ‘split’ of a dinuclear complex. The
results of the ethylene polymerizations with these
reference catalysts are shown in Scheme 15.
As a general observation, it was found that the
catalyst activity increases from cyclopentadienyl to
fluorenyl substitution. The mixtures are in the same
range as the single site catalysts. On the other hand,
heterogenization on silica gel causes a decrease of
activity. The phenyl-substituted catalysts produce higher
molecular masses of the polymers and have a slightly
higher productivity. The polydispersities of the poly-
The mononuclear reference complexes R1ꢀ
/R6 were
activated with MAO and polymerized under homoge-

H.G. Alt, R. Ernst / Inorganica Chimica Acta 350 (2003) 1ꢀ
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11
5
Scheme 13. HT-GPC plot of polyethylene produced with 33 under heterogeneous conditions.
of ethylene with catalyst mixtures are known and show
similar results [31ꢀ36].
/
The difference between two dinuclear complexes is
caused by the different chain lengths of the spacer units
between the two metal centers. This is an indication for
a cooperative effect of the two metal centers that must
also be dependent from the steric conditions during the
polymerization process. As a consequence, the average
values of the catalyst activities and the polydispersities
of the formed polymers were calculated and compared
with the performance of the mixture of the mononuclear
catalysts.
Scheme 17 shows the catalyst activities of the three
catalyst reference mixtures and the averaged activities of
the cyclopentadienyl, indenyl and fluorenyl substituted
catalysts. It is obvious that the dinuclear catalysts
increase their activities after heterogenization. This is
rather uncommon. In case of mononuclear species, the
opposite effect is observed. On the other hand, the
activities of the dinuclear catalysts are generally lower
Scheme 14. Splitting of a dinuclear metallocene complex into two
mononuclear complexes.
ethylenes produced with the reference catalysts are
shown in Scheme 16:
It becomes obvious that catalyst mixtures produce
polymers with a higher HI than the single site catalysts.
This broadening effect increases in the series cy-
clopentadienylB
/
indenylBfluorenyl. Polymerizations
/
Scheme 15. Activities of the reference catalysts R1ꢀR6 and mixtures thereof.
/

6
H.G. Alt, R. Ernst / Inorganica Chimica Acta 350 (2003) 1ꢀ11
/
Scheme 16. Polydispersities of the reference catalysts R1ꢀR6 and mixtures thereof.
/
under homogeneous conditions. The polydispersities are
presented in Scheme 18.
C6H5CH3) was supplied by Witco Company, Bergka-
men. All the other starting materials were commercially
available and were used without further purification.
The effects that contribute to the amount of the
polydispersities are not as clear as in the case of the
activities, but a good tendency can be anticipated: The
average molecular mass distribution of the polymers
produced with dinuclear catalysts is decreasing with
growing size of the ligands from cyclopentadienyl to
fluorenyl substitution. The polymers produced with
catalyst mixtures show an opposite effect. The larger
the ligands the higher the results of the polydispersity. It
seems that a larger ligand sphere in case of mononuclear
catalysts has a much stronger impact on the catalyst
properties than in the case of a dinuclear catalyst.
3.1. NMR spectroscopy
The spectrometer Bruker ARX 250 was available for
the recording of the NMR spectra. The organometallic
compounds were prepared under inert gas atmosphere
(Ar). The spectra were recorded at 25 8C. The chemical
shifts in the 1H NMR spectra are referred to the residual
proton signal of the solvent (dꢂ
dꢂ
7.15 ppm for C6H6) and in the 13C NMR spectra to
the solvent signal (dꢂ77.0 ppm for CHCl3-d1, dꢂ128.0
0.0 ppm) was
/7.24 ppm for CHCl3,
/
/
/
ppm for C6H6-d6). Tetramethylsilane (dꢂ
/
used as external calibration for 29Si NMR spectra.
3. Experimental
All experimental work was routinely carried out using
Schlenk technique. Dried and purified Ar was used as
inert gas. Toluene, C5H12, Et2O and THF were purified
by distillation over Na/K alloy. Ether was additionally
distilled over LiAlH4. Methylene chloride was dried with
CaH2. Deuterated solvents such as CHCl3-d1 and C6H6-
d6 were dried over molecular sieves (300 pm), degassed
and stored under inert gas atmosphere.
3.2. GC/MS spectroscopy
GC/MS spectra were performed with a HP5971A
mass detector in combination with a HP5890 gas
chromatograph. Helium was applied as carrier gas, a
12 m J&W Fused Silica column (DB 1, film thickness
0.25 mm) was used. The measuring program was: 3 min
at 70 8C (starting phase); 20 8C minꢃ1 (heating phase);
variable time at 210 8C (final phase).
Commercially available indene was distilled and
stored at ꢃ28 8C. Cyclopentadiene was freshly distilled
/
from the dimer. Methylalumoxane (MAO; 30% in
Scheme 17. Comparison of catalyst activities of catalyst mixtures and
dinuclear catalysts.
Scheme 18. Polydispersities of polyethylenes produced with catalyst
mixtures and with dinuclear catalysts.

H.G. Alt, R. Ernst / Inorganica Chimica Acta 350 (2003) 1ꢀ
/
11
7
3.3. Mass spectroscopy
3.8. Preparation of v-octenyl methyl dichlorosilane by
hydrosilation reaction
The mass spectra were recorded with a VARIAN
MAT CH7 instrument, GC/MS with a VARIAN 3700
gas chromatograph in combination with a VARIAN
MAT 312 mass spectrometer.
1,7-Octadiene (11 g, 100 mmol), hexachloroplatinic
acid hydrate (30ꢀ50 mg) and C5H12 (10 ml) were given
/
to a Schlenk vessel. Dichloromethylsilane (30 mmol)
was added and this mixture was stirred for 20 h. After
filtration (Na2SO4 filled filter column) the solvent and
the excess amount of 1,7-octadiene were removed in
vacuo. The crude product was distilled in vacuo. Yield:
95%.
3.4. Gas chromatography
Gas chromatograms were recorded using a Perkinꢀ
/
Elmer Auto System gas chromatograph with flame
ionization detector (FID) and He as carrier gas (1 ml
minꢃ1).
3.9. Preparation of the alkyl, aryl or v-alkenyl
Temperature program:
substituted dichlorosilane derivatives 1ꢀ
/
6 by Grignard
reaction
Starting phase: 3 min at 50 8C
Heating phase: 5 8C minꢃ1 (15 min)
Plateau phase: 310 8C (15 min)
Magnesium turnings (6.1 g, 250 mmol) suspended in
100 ml of Et2O were placed in a three necked flask with
dropping funnel and reflux cooling system at 0 8C. The
Mg was activated by addition of 0.1 g I2. Alkyl, aryl or
v-alkenyl bromide (240 mmol) in 100 ml of ether were
added slowly during 1 h. After addition of the bromide
the mixture was stirred for another hour at room
temperature (r.t.).
3.5. High temperature gel permeation chromatography
(HT-GPC)
A Waters HT-GPC 150C instrument was applied to
measure the mass distributions of the polymer samples.
Four columns filled with cross-linked polystyrene were
used for separation of the fractions. The pore diameters
Trichlorosilane derivative (70 ml, 450 mmol) in 100
ml of Et2O was placed in a Schlenk vessel. The Grignard
˚
of the styragels were 500, 1000, 10 000 and 100 000 A in
product was added slowly to this mixture at ꢃ78 8C
/
the individual columns. A RI Waters 401 refractometer
was used for detection. The polymer samples were
dissolved in boiling 1,2,4-trichlorobenzene that was
also used as eluent. The measurements were carried
out at 150 8C. The apparatus was calibrated with an
internal polystyrene standard.
within 1 h and brought to r.t. within 3 h. The solvent
and the excess trichlorosilane were distilled off the
mixture. The residue was suspended in C5H12, the
solution filtered over Na2SO4 and the crude product
was distilled. Yields: 50ꢀ80%. The products were
/
characterized by NMR spectroscopy (Table 2).
3.6. Preparation of v-bromo-1-alkenes by elimination
reaction
3.10. Preparation of cyclopentadienyl substituted ligand
precursors
a,v-Dibromoalkane (440 mmol) was heated to
200 8C. Hexamethylphosporic acid triamide (HMPT,
240 mmol) was added slowly. The resulting v-bromo-1-
alkenes were distilled off the reaction mixture and
purified by another distillation at normal pressure.
Sodium cyclopentadienyl (4.5 g, 51.1 mmol) in 50 ml
of THF was placed in a Schlenk vessel. 2-Sila-2,2-
dichloro-5-hexene (4.32 g, 25.6 mmol) was added and
the mixture was stirred for 15 h at r.t. The solvent was
removed in vacuo and the residue was suspended in
Et2O. The suspension was filtered over Na2SO4/SiO2
Yields: 40ꢀ60%.
/
and the solvent was removed in vacuo. Yields: 70ꢀ80%.
/
3.7. Preparation of alkyl, aryl or v-alkenyl substituted
dichlorosilane derivatives by hydrosilation reaction
3.11. Preparation of indenyl or fluorenyl substituted
ligand precursors
a,v-Alkadiene (150 mmol) was dissolved in 5 ml of
C5H12 and treated with 30ꢀ50 mg hexachloroplatinic
/
acid hydrate. Dichloromethylsilane (50 mmol) was
added and this mixture was stirred for 40 h. After
filtration (Na2SO4 filled filter column) the solvent and
the excess amount of a,v-alkadiene were removed in
vacuo. The crude product was distilled in vacuo. Yields:
Indenyl lithium or fluorenyl lithium (23.4 mmol) in
100 ml of Et2O was placed in a Schlenk vessel. 2-Sila-
2,2-dichloro-v-alkene (25.6 mmol) dissolved in 10 ml of
Et2O was added and the mixture was stirred for 8 h at
r.t. The suspension was filtered over Na2SO4/SiO2 and
70ꢀ/80%.
the solvent was removed in vacuo. Yields: 60ꢀ70%.
/

8
H.G. Alt, R. Ernst / Inorganica Chimica Acta 350 (2003) 1ꢀ11
/
Table 2
NMR data a of compounds 1ꢀ
44
/
Compound 1H NMR
13C NMR
n.d.
29Si NMR
1
2
n.d.
5.87ꢀ
CH2), 2.12ꢀ
CH3)
5.79ꢀ
CH2), 2.11ꢀ
(s, 3H, SiÃCH3)
5.67ꢀ5.54 (m, 1H, vinyl-CH), 4.89ꢀ
CH2), 2.08ꢀ1.92, 1.47ꢀ1.40, 0.97ꢀ0.91 (m, 6H, pente- pentenyl-substituent), 5.4 (SiÃ
nyl-CH2), 0.57 (s, 3H, SiÃCH3)
n.d.
28.1
/5.58 (m, 1H, vinyl-CH), 5.11ꢀ
/
5.05 (m, 2H, vinyl- 129.6 (vinyl-CH), 118.9 (vinyl-CH2), 28.4 (CH2, allyl-
substituent), 4.4 (SiÃCH3)
/
2.05 (d, 2H, allyl-CH2), 0.76 (s, 3H, SiÃ
/
/
3
4
/
5.68 (m, 1H, vinyl-CH), 5.09ꢀ
/
4.92 (m, 2H, vinyl- 138.9 (vinyl-CH), 114.5 (vinyl-CH2), 33.9, 21.7 (CH2,
CH3)
32.8
/
2.07, 1.35ꢀ0.89 (m, 4H, butenyl-CH2), 0.45 butenyl-substituent), 5.0 (SiÃ
/
/
/
/
/
4.77 (m, 2H, vinyl- 139.3 (vinyl-CH), 115.8 (vinyl-CH2), 36.4, 29.1, 22.0 (CH2, 33.0
CH3)
/
/
/
/
/
5
6
7
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
7.49ꢀ
/
7.45, 7.24ꢀ
/
7.20 (m, 5H, Ph), 1.24ꢀ
/
1.17, 1.02ꢀ
/
0.95 133.6, 132.2, 128.6 (CH, Ph), 130.8 (Cq, Ph), 13.8, 12.5
33.1 (MeÃ
19.3 (PhÃSi)
/Si)
(m, 4H, bridge), 0.52 (s, 3H, SiÃ
/
CH3)
(CH2, bridge), 3.9 (SiÃCH3)
/
/
8
7.68ꢀ7.64, 7.18ꢀ7.08 (m, 5H, Ph), 1.75ꢀ
0.89ꢀ0.82 (m, 6H, bridge), 0.39 (s, 3H, SiÃ
7.87ꢀ7.65, 7.46ꢀ7.38 (m, 5H, Ph), 1.78ꢀ1.17 (m, 8H,
bridge), 0.79 (s, 3H, SiÃCH3)
7.59ꢀ7.55, 7.33ꢀ7.27 (m, 5H, Ph), 1.43ꢀ
(m, 10H, bridge), 0.59 (s, 3H, SiÃCH3)
7.67ꢀ7.64, 7.18ꢀ7.10 (m, 5H, Ph), 1.89ꢀ
(m, 12H, bridge), 0.42 (s, 3H, SiÃCH3)
7.57ꢀ7.55, 7.30ꢀ7.27 (m, 5H, Ph), 1.22ꢀ
(m, 16H, bridge), 0.59 (s, 3H, SiÃCH3)
/
/
/
1.69, 1.19ꢀ
/
1.12, 133.4, 132.0, 128.7 (CH, Ph), 132.2 (Cq, Ph), 34.1, 22.4,
31.8 (MeÃSi)
18.5 (PhÃSi)
32.8 (MeÃSi)
19.7 (PhÃSi)
33.0 (MeÃSi)
19.2 (PhÃSi)
33.1 (MeÃSi)
19.4 (PhÃSi)
33.2 (MeÃSi)
19.1 (PhÃSi)
/
/
/CH3)
21.8 (CH2, bridge), 4.9 (SiÃCH3)
/
/
9
/
/
/
133.4, 130.8, 129.0 (CH, Ph), 132.1 (Cq, Ph), 34.5, 24.1,
21.7, 14.5 (CH2, bridge), 4.1 (SiÃCH3)
/
/
/
/
10
11
12
/
/
/
1.33, 1.21ꢀ
/1.15 133.6, 131.9, 128.6 (CH, Ph), 132.6 (Cq, Ph), 35.2, 22.3,
/
/
20.7 (CH2, bridge), 5.5 (SiÃCH3)
/
/
/
/
/
1.03, 0.81ꢀ
/0.72 134.1, 132.0, 129.9 (CH, Ph), 133.1 (Cq, Ph), 33.0, 27.4,
/
/
25.6, 20.7, 18.2, 15.5 (CH2, bridge), 5.0 (SiÃCH3)
/
/
/
/
/
1.07, 0.96ꢀ
/
0.70 133.3, 131.5, 128.3 (CH, Ph), 132.4 (Cq, Ph), 32.3, 32.2,
28.8, 28.7, 22.4, 21.6, 21.5, 20.6 (CH2, bridge), 5.2 (SiÃ
CH3)
/
/
/
/
13
14
15
16
17
7.45ꢀ
/
7.33 (m, 5H, Ph), 6.69ꢀ
/
6.33 (m, 16H, ar H, Cp), 138.6, 134.5, 132.7, 131.1, 129.4, 127.6, 117.4 (CH, ar, Cp, 5.6 (MeÃ
2.98 (m, 8H, al H, Cp), 1.25ꢀ0.30 (m, 4H, bridge), Ph), 136.2, 128.1 (Cq, Cp, Ph), 46.9, 44.2 (CH2, al, Cp), 6.0 (PhÃ
0.01, ꢃ0.27 (s, 3H, SiÃCH3) 21.9, 20.8 (CH2, bridge), ꢃ6.5, ꢃ6.9 (SiÃCH3)
/
Si)
3.60ꢀ
/
/
ꢃ/
/Si)
ꢃ/
/
/
/
/
/
7.68ꢀ7.21 (m, 5H, Ph), 6.98ꢀ6.92, 6.22ꢀ5.87 (m, 16H, 142.5, 141.9, 140.0 (Cq, Cp, Ph), 134.5, 133.9, 132.9, 131.1,
ar H, Cp), 3.93ꢀ3.67 (m, 8H, al H, Cp), 1.32ꢀ0.52 (m, 129.3, 127.6 (CH, Cp, Ph), 47.8 (CH2, al, Cp), 26.8, 8.9,
6H, bridge), 0.12, ꢃ0.07 (s, 3H, SiÃCH3) 8.6 (CH2, bridge), ꢃ4.4 (SiÃCH3)
7.71ꢀ7.17 (m, 5H, Ph), 6.95ꢀ6.78, 6.43ꢀ5.91 (m, 16H, 144.4, 144.0, 140.6 (Cq, Cp, Ph), 134.8, 133.8, 133.4, 133.0,
ar H, Cp), 3.90ꢀ3.81 (m, 8H, al H, Cp), 1.73ꢀ0.55 (m, 131.4, 130.6, 129.8, 128.1 (CH, Cp, Ph), 46.3 (CH2, al,
8H, bridge), ꢃ0.09, ꢃ0.26 (s, 3H, SiÃCH3) Cp), 25.4, 23.4, 12.9, 10.8 (CH2, bridge), ꢃ5.8 (SiÃCH3)
7.83ꢀ7.29 (m, 5H, Ph), 7.01ꢀ6.95, 6.32ꢀ5.91 (m, 16H, 142.4, 142.0, 140.5 (Cq, Cp, Ph), 133.7, 132.9, 132.2, 131.0,
ar H, Cp), 3.85ꢀ3.71 (m, 8H, al H, Cp), 1.92ꢀ0.42 (m, 130.3, 127.2 (CH, Cp, Ph), 46.4 (CH2, al, Cp), 28.3, 18.8,
10H, bridge), 0.09, ꢃ0.13 (s, 3H, SiÃCH3) 17.4, 9.1, 8.8 (CH2, bridge), ꢃ5.2 (SiÃCH3)
7.65ꢀ7.34 (m, 5H, Ph), 6.78ꢀ6.43 (m, 16H, ar H, Cp), 143.1, 142.7, 139.6 (Cq, Cp, Ph), 135.1, 134.8, 134.1, 133.2, 3.2 (MeÃ
3.82ꢀ3.03 (m, 8H, al H, Cp), 2.22ꢀ0.61 (m, 10H, 131.4, 130.8, 130.1, 128.2 (CH, Cp, Ph), 46.9 (CH2, al, 7.9 (PhÃ
bridge), 0.21, 0.06, ꢃ0.15 (s, 3H, SiÃCH3) Cp), 33.4, 24.4, 23.4, 13.6, 11.5, 11.0 (CH2, bridge), ꢃ0.1,
6.5 (SiÃCH3)
6.21 (m, 16H, ar H, Cp), 145.2, 145.0, 144.5, 141.1, 140.8 (Cq, Cp, Ph), 134.5, 134.0, 4.2 (MeÃ
/
/
/
ꢃ
/
2.6 (MeÃ
/Si)
/
/
ꢃ13.7 (PhÃ
/
/
Si)
/
/
/
/
/
/
/
ꢃ
/
2.9 (MeÃ
/Si)
/
/
ꢃ13.3 (PhÃ
/
/
Si)
/
/
/
/
/
/
/
/
ꢃ
/
2.5 (MeÃ
/Si)
/
/
ꢃ13.7 (PhÃ
/
/
Si)
/
/
/
/
/
/
/Si)
/
/
ꢃ/
/
Si)
/
/
/
ꢃ/
/
18
7.58ꢀ
3.96ꢀ
bridge), ꢃ
/
7.18 (m, 5H, Ph), 6.53ꢀ
2.89 (m, 8H, al H, Cp), 1.99ꢀ
0.24, ꢃ0.37 (s, 3H, SiÃCH3)
/
/Si)
/
/
0.96 (m, 16H,
129.1, 129.0, 128.0, 126.0, 125.6, 124.5, 124.0, 120.0, 119.9,
119.8, 119.7 (CH, ar, Cp, Ph), 40.4, 39.7, 38.5 (CH, al,
Cp), 33.4, 33.2, 28.3, 26.6, 25.6, 23.1, 22.7, 11.6, 10.6, 10.4,
ꢃ
(PhÃSi)
/
7.2, ꢃ
/
/
7.4
/
/
/
9.0 (CH2, bridge), ꢃ
6.21 (m, 29H, ar Ind, Ph), 3.81, 3.76, 3.56 (m, 4H, n.d.
al H, Ind), 3.02 (s, 4H, al H, Ind), 0.13, ꢃ0.16, ꢃ0.31 (s,
3H, SiÃCH3)
7.21ꢀ6.22 (m, 29H, ar H, Ind, Ph), 3.91ꢀ
(m, 8H, al H, Ind), 1.39ꢀ1.10, 0.90ꢀ0.81 (m, 6H,
bridge), ꢃ0.14, ꢃ0.32 (s, 3H, SiÃCH3)
/
6.3, ꢃ
/
7.1 (SiÃCH3)
/
19
20
7.39ꢀ
/
6.1 (MeÃ
4.9 (PhÃ
/
Si)
/
/
ꢃ/
/Si)
/
/
/
3.43, 3.03ꢀ
/
3.00 144.4, 144.0, 142.1 (Cq, Ind, Ph), 133.8, 129.9, 127.8, 127.4, 4.1 (MeÃ
124.1, 123.7, 121.4 (CH, Ind, Ph), 42.6, 40.9, (CH, al, Ind),
38.8 (CH2, al, Ind), 27.3, 27.1, 19.6 (CH2, bridge), ꢃ1.6
(SiÃCH3)
/
Si)
/
/
ꢃ
/
4.2 (PhÃSi)
/
/
/
/
/
/

H.G. Alt, R. Ernst / Inorganica Chimica Acta 350 (2003) 1ꢀ
/
11
9
Table 2 (Continued)
Compound 1H NMR
13C NMR
29Si NMR
21
22
7.51ꢀ
(m, 4H, al H, Ind), 1.25ꢀ
(s, 3H, SiÃCH3)
/
7.31, 7.22ꢀ
/
6.50 (m, 29H, ar H, Ind, Ph), 3.54ꢀ
/
3.39 145.2, 145.1, 144.8, 140.1 (Cq, Ind, Ph), 135.6, 134.4, 134.0, 5.7 (MeÃ
/
Si)
/
0.91 (m, 10H, bridge), ꢃ
/
0.29 131.8, 130.4, 129.6, 129.4, 128.1, 124.7, 123.4, 121.7, 121.5
(CH, ar, Ind, Ph), 47.8, 46.6, 45.6, 44.8 (CH, al, Ind), 30.0,
ꢃ/
4.4 (PhÃSi)
/
/
29.9, 24.8, 22.8, 22.7 (CH2, bridge), ꢃ
6.74, 6.28, 6.23 (m, 29H, ar H, Ind, Ph), 145.2, 144.9, 143.9, 143.2 (Cq, Ind, Ph), 133.4, 132.6, 131.7, 6.1, 5.7 (MeÃ
3.05 (m, 8H, al H, Cp), 2.21ꢀ0.37 (m, 12H, 130.8, 130.6, 129.3, 128.5, 128.4, 128.1, 127.9, 127.6, 126.2, 5.0, ꢃ5.3
bridge), ꢃ0.08, ꢃ0.11, ꢃ0.30 (s, 3H, SiÃCH3) 123.1 (CH, ar, Ind, Ph), 47.7, 44.4, 41.4, 39.1 (CH, al, Ind), (PhÃSi)
33.1, 33.0, 27.0, 26.5, 14.2, 13.6 (CH2, bridge), 0.1, ꢃ5.9
(SiÃCH3)
6.72 (m, 31H, Ind, Ph), 3.63, 3.51, 3.38 (s, 8H, al h, 144.4, 143.6, 142.6 (Cq, Ind, Ph), 135.2, 134.1, 132.0, 129.5, 5.9 (MeÃ
Ind), 1.35ꢀ0.51 (m, 16H, bridge), 0.07, ꢃ0.16, ꢃ0.30 (s, 129.4, 127.7, 126.8, 126.2, 124.8, 124.5, 123.6, 122.7, 121.2, 4.6, ꢃ4.8
3H, SiÃCH3) 121.0, 120.9, (CH, ar, Ind, Ph), 51.8, 50.6, 44.3, 44.0 (CH, (PhÃSi)
al, Ind), 39.0 (CH2, al, Ind), 33.3, 33.1, 32.9, 29.7, 29.5,
29.3, 29.0, 22.9, 22.8 (CH2, bridge), ꢃ6.2 (SiÃCH3)
6.83 (m, 37H, ar H, Flu, Ph), 4.42, 3.92 (s, 4H, al n.d.
H, Flu), 3.18ꢀ3.14, 2.26ꢀ2.17 (m, 4H, bridge), ꢃ0.36,
0.38, ꢃ0.71 (s, 3H, SiÃCH3)
7.62ꢀ7.38 (m, 5H, Ph), 7.38ꢀ6.63 (m, 32H, Flu), 4.24, 143.8, 142.9, 142.1, 140.1 (Cq, Flu, Ph), 135.3, 128.3, 127.6, 0.8 (MeÃ
3.52 (s, 4H, al H, Flu), 1.34ꢀ1.19 (m, 6H, bridge), 0.11 127.0, 126.2, 124.9, 120.5 (CH, Flu, Ph), 38.3, 38.1 (CH,
(s, 3H, SiÃCH3) al, Flu), 27.3, 26.8, 22.1 (CH2, bridge), 0.1 (SiÃCH3)
7.82ꢀ7.45 (m, 5H, Ph), 7.18ꢀ6.70 (m, 32H, Flu), 4.03, 144.6, 144.1, 142.1, 140.0 (Cq, Flu, Ph), 135.3, 134.7, 131.0, 0.8 (MeÃ
3.72 (s, 4H, al H, Flu), 1.56ꢀ
0.17 (s, 3H, SiÃCH3)
/
6.5 (SiÃ
/
CH3)
7.44ꢀ
/
7.12, 6.77ꢀ
/
/Si)
3.82ꢀ
/
/
ꢃ/
/
/
/
/
/
/
/
/
23
7.68ꢀ
/
/
Si)
/
/
/
ꢃ/
/
/
/
/
/
24
25
26
7.87ꢀ
/
8.2 (MeÃ
/
Si)
/
/
/
ꢃ
/
3.8 (PhÃ
/Si)
ꢃ/
/
/
/
/
/
Si)
/
ꢃ
/
8.8 (PhÃ
/Si)
/
/
/
/
/
Si)
/
1.07 (m, 10H, bridge), ꢃ
/
128.2, 127.2, 126.9, 126.3, 125.0, 123.4, 120.5 (CH, Flu,
Ph), 39.9, 38.6 (CH, al, Flu), 29.6, 27.3, 26.8, 22.1, 19.4
ꢃ
/
8.5 (PhÃ
/Si)
/
(CH2, bridge), ꢃ
/
0.2 (SiÃ/CH3)
27
28
7.78ꢀ
4H, al H, Flu), 1.98ꢀ
3H, SiÃCH3)
/
7.44 (m, 5H, Ph), 7.05ꢀ
/
6.57 (m, 32H, Flu), 3.81 (s, 143.9, 143.0, 142.4, 139.7 (Cq, Flu, Ph), 135.3, 134.3, 131.7, 7.9 (MeÃ
/
Si)
/0.56 (m, 12H, bridge), ꢃ
/
0.05 (s, 128.9, 128.1, 127.8, 126.6, 126.1, 125.0, 121.5, 120.5 (CH,
Flu, Ph), 39.3 (CH, al, Flu), 32.1, 30.0, 27.3, 26.8, 22.1,
ꢃ/
4.0 (PhÃ
/Si)
/
17.2 (CH2, bridge), 0.0 (SiÃ
/CH3)
7.82ꢀ
4.53, 3.99 (s, 4H, al H, Flu), 1.39ꢀ
0.23, ꢃ0.52 (s, 3H, SiÃCH3)
/7.53 (m, 5H, Ph), 7.38ꢀ
/
6.41 (m, 32H, ar H, Flu), 145.8, 145.7, 141.2, 140.8, 131.6 (Cq, Flu, Ph), 134.5, 134.4, 7.1 (MeÃ
/
Si)
/
0.20 (m, 16H, bridge), 127.6, 126.7, 126.2, 125.9, 125.8, 125.6, 125.5, 125.2, 124.6,
124.2, 124.2, 120.1, 120.0, 119.8, 119.7 (CH, ar, Flu, Ph),
ꢃ/
0.1 (PhÃSi)
/
ꢃ/
/
/
40.8, 40.4, 39.7, 38.7 (CH, al H, Flu), 33.4, 33.2, 29.9, 28.4,
28.3, 26.6, 25.9, 23.6, 23.4, 22.7 (CH2, bridge), ꢃ
/
5.2, ꢃ7.1
/
(SiÃCH3)
/
29
30
31
32
33
34
7.93ꢀ
Cp), 1.57ꢀ
SiÃCH3)
/
7.38 (m, 5H, Ph), 6.98ꢀ
/
6.83, 6.38ꢀ
/
6.27 (m, 16H, 144.4, 143.3, 139.9, (Cq, Cp, Ph), 135.1, 129.8, 129.6,
0.82 (m, 4H, bridge), 0.02 (s, 3H, 129.0, 128.6, 127.6, 115.5, 114.9, 113.2 (CH, Cp, Ph), 12.1,
11.4 (CH2, bridge), ꢃ5.9 (SiÃCH3)
ꢃ
/
11.6 (MeÃ
/
Si)
/
1.31, 0.99ꢀ
/
ꢃ
/
22.1 (PhÃSi)
/
/
/
/
7.62ꢀ7.54, 7.30ꢀ
/
/
7.23, 6.87ꢀ/6.83 (m, 21H, Cp, Ph),
145.2, 141.6, 140.6 (Cq, Cp, Ph), 135.1, 131.4, 130.7, 130.0,
129.0, 126.9, 116.3, 114.6, 113.9 (CH, Cp, Ph), 27.1, 16.6,
ꢃ
/
13.5 (MeÃ
/
Si)
1.52ꢀ0.81 (m, 6H, bridge), 0.17 (s, 3H, SiÃ
/
/CH3)
ꢃ23.8 (PhÃSi)
/
/
14.0 (CH2, bridge), ꢃ
/
7.5 (SiÃCH3)
/
7.99ꢀ/6.00 (m, 21H, Cp, Ph), 1.83ꢀ
/
1.49 (m, 6H, bridge), 147.1, 144.8, 144.7 (Cq, Cp, Ph), 134.9, 131.4, 129.2, 128.8,
127.9, 115.6, 115.0, 113.8 (CH, Cp, Ph), 26.4, 11.3, 11.2
ꢃ
/
12.3 (MeÃ
/
Si)
0.19 (s, 3H, SiÃ
/CH3)
ꢃ21.7 (PhÃSi)
/
/
(CH2, bridge), ꢃ
5.92 (m, 16H, 144.5, 144.1, 140.5 (Cq, Cp, Ph), 134.9, 133.4, 130.6, 129.2,
0.62 (m, 10H, bridge), 0.09 (s, 3H, SiÃCH3) 128.8, 127.9, 127.6, 115.6, 115.0, 113.8 (CH, Cp, Ph), 29.8,
23.4, 22.7, 11.3, 11.2 (CH2, bridge), ꢃ6.9 (SiÃCH3)
/
7.2 (SiÃ/CH3)
7.87ꢀ/7.27 (m, 5H, Ph), 6.98ꢀ
/
6.90, 6.22ꢀ
/
ꢃ
/
12.1 (MeÃ
/
Si)
Cp), 1.87ꢀ
/
/
ꢃ23.2 (PhÃSi)
/
/
/
/
7.75ꢀ/7.30 (m, 5H, Ph), 6.90ꢀ
/
6.03 (m, 16H, Cp), 2.12ꢀ
/
145.2, 139.8, 137.6 (Cq, Cp, Ph), 129.8, 129.2, 128.9, 128.2,
116.0, 115.9, 114.2, 114.1 (CH, ar, Cp, Ph), 32.9, 26.8,
ꢃ
/
12.3 (MeÃ
/
Si)
0.59 (m, 12H, bridge), 0.02 (s, 3H, SiÃ
/CH3)
ꢃ21.9 (PhÃSi)
/
/
26.4, 22.9, 11.6, 11.1 (CH2, bridge), ꢃ
144.2, 140.8, 140.1 (Cq, Cp, Ph), 135.1, 133.9, 130.2, 129.8,
0.12 (s, 129.2, 128.9, 128.2, 115.9, 114.2 (CH, ar, Cp, Ph), 32.9,
31.0, 28.5, 26.8, 26.4, 22.9, 11.6, 11.1 (CH2, bridge), ꢃ7.2
SiÃCH3)
5.77 146.2, 144.7, 134.1, 134.0 (Cq, Ind, Ph), 132.5, 128.5, 127.6,
0.86 (m, 4H, bridge), 0.03 (s, 3H, 126.7, 122.1, 105.2, 104.0 (CH, Ind, Ph), 15.1, 12.9 (CH2,
bridge), ꢃ6.1 (SiÃCH3)
/
7.8 SiÃ/CH3)
7.63ꢀ
2.46, 2.19ꢀ
3H, SiÃCH3)
/7.22 (m, 5H, Ph), 6.81ꢀ
/
6.23 (m, 16H, Cp), 2.66ꢀ
/
ꢃ
/
10.9 (MeÃ
/
Si)
/
1.73, 1.45ꢀ0.59 (m, 16H, bridge), ꢃ
/
/
ꢃ21.5 (PhÃSi)
/
/
/
/
/
35
7.77ꢀ
(m, 24H, Ind), 1.39ꢀ
SiÃCH3)
/7.61 (m, 5H, Ph), 7.36ꢀ
/
6.90, 6.12ꢀ
/
6.10, 5.81ꢀ
/
ꢃ
/
11.6 (MeÃ
/
Si)
/
ꢃ21.5 (PhÃSi)
/
/
/
/
/

10
H.G. Alt, R. Ernst / Inorganica Chimica Acta 350 (2003) 1ꢀ11
/
Table 2 (Continued)
Compound 1H NMR
13C NMR
29Si NMR
36
7.75ꢀ
/
7.62 (m, 5H, Ph), 7.33ꢀ
/
6.76 (m, 24H, Ind), 1.31ꢀ
/
145.1, 144.0, 140.2 (Cq, Ind, Ph), 132.5, 131.6, 129.7, 129.1,
128.5, 127.6, 126.7, 122.1, 105.2, 104.0 (CH, Ind, Ph), 23.0,
ꢃ
/
9.3 (MeÃ
/
Si)
0.29 (m, 6H, bridge), 0.11 (s, 3H, SiÃ
/
CH3)
ꢃ20.1 (PhÃ
/
/Si)
15.1, 12.9 (CH2, bridge), ꢃ
/
6.4 (SiÃCH3)
/
37
7.69ꢀ
0.11 (s, 3H, SiÃ
/
6.73 (m, 29H, Ind, Ph), 1.41ꢀ
/
0.67 (m, 4H, bridge), 144.7, 144.0, 140.9, 140.2 (Cq, Ind, Ph), 135.0, 132.5, 131.6,
129.7, 129.1, 128.5, 127.6, 126.7, 122.1, 120.3, 115.2, 114.0
ꢃ
/
11.9 (MeÃ
/
Si)
/
CH3)
ꢃ21.3 (PhÃSi)
/
/
(CH, Ind, Ph), 29.0, 23.0, 22.7, 12.1, 11.9 (CH2, bridge), ꢃ
/
6.8 (SiÃCH3)
/
38
39
7.89ꢀ
/
6.73 (m, 29H, Ind, Ph), 2.05ꢀ
/
1.67, 1.41ꢀ
/
0.67 (m, 144.8, 144.0, 141.0, 140.1 (Cq, Ind, Ph), 135.0, 132.3, 131.1,
130.0, 129.5, 128.6, 127.2, 126.8, 122.0, 120.8, 115.1, 113.9
(CH, Ind, Ph), 31.5, 30.7, 29.0, 22.7, 12.1, 11.9 (CH2,
ꢃ
/
11.7 (MeÃ
/
Si)
12H, bridge), 0.03 (s, 3H, SiÃ
/CH3)
ꢃ
/
22.1 (PhÃSi)
/
bridge), ꢃ
/
7.0 (SiÃCH3)
/
7.91ꢀ
/
6.99, 6.58ꢀ
0.72 (m, 16H, bridge), 0.09 (s, 3H, SiÃ
/6.49, 6.19ꢀ/6.13 (m, 29H, Ind, Ph),
147.0, 146.8, 144.5, 144.3 (Cq, Ind, Ph), 135.9, 135.2, 134.2,
129.1, 127.6, 124.9, 124.4, 123.8, 123.6, 122.6, 122.2, 121.0
(CH, Ind, Ph), 29.7, 29.0, 26.7, 26.0, 23.8, 22.4, 9.6, 9.4
ꢃ
/
11.6 (MeÃ
/
Si)
1.68ꢀ
/
/CH3)
ꢃ20.4 (PhÃSi)
/
/
(CH2, bridge), ꢃ
/
6.4 (SiÃCH3)
/
40
41
42
43
7.81ꢀ
4H, bridge), ꢃ
/
7.58, 7.46ꢀ
/
7.01 (m, 37H, Flu, Ph), 2.21ꢀ
/
0.93 (m, 144.5, 144.0, 140.1 (Cq, Flu, Ph), 135.0, 133.4, 130.1, 129.0,
128.1, 127.9, 127.4, 126.8, 126.2, 125.5, 125.1, 124.7, 124.2
ꢃ
/
11.2 (MeÃ
/
Si)
/
0.01 (s, 3H, SiÃ
/CH3)
ꢃ
/
21.0 (PhÃSi)
/
(CH, Flu, Ph), 14.2, 12.4 (CH2, bridge), ꢃ
/
6.7 (SiÃCH3)
/
7.87ꢀ
/
7.47, 7.36ꢀ
/
6.91 (m, 37H, Flu, Ph), 2.01ꢀ
/
0.52 (m, 145.0, 144.4, 140.9, 131.4 (Cq, Flu, Ph), 134.0, 129.0, 127.5,
127.0, 126.6, 126.1, 124.5, 124.2, 120.0 (CH, Flu, Ph), 25.3,
ꢃ
/
11.2 (MeÃ
/
Si)
6H, bridge), ꢃ
/
0.15 (s, 3H, SiÃ
/CH3)
ꢃ20.9 (PhÃSi)
/
/
11.0, 8.5 (CH2, bridge), ꢃ
/
7.0 (SiÃCH3)
/
7.91ꢀ
1.38ꢀ
SiÃCH3)
/
7.62, 7.51ꢀ
0.93, 0.65ꢀ
/
7.10 (m, 37H, Flu, Ph), 2.21ꢀ
0.23 (m, 10H, bridge), ꢃ0.01 (s, 3H,
/
1.56,
144.5, 144.0, 140.1 (Cq, Flu, Ph), 135.0, 133.4, 130.1, 129.0,
128.1, 127.9, 127.4, 126.8, 126.2, 125.5, 125.1, 124.7, 124.2
ꢃ
/
12.4 (MeÃ
/
Si)
/
/
/
ꢃ22.6 (PhÃSi)
/
/
/
(CH, Flu, Ph), 14.2, 12.4 (CH2, bridge), ꢃ
/
6.7 (SiÃCH3)
/
7.79ꢀ7.65, 7.40ꢀ
/
/
7.19, 7.03ꢀ
/6.64 (m, 37H, Flu, Ph),
146.0, 145.4, 141.0, 131.7 (Cq, Flu, Ph), 134.1, 129.1, 128.5,
127.5, 126.7, 126.2, 125.7, 125.3, 124.6, 124.2, 120.2, 120.0
(CH, Flu, Ph), 33.4, 33.3, 23.6, 23.3, 11.7, 9.3 (CH2,
ꢃ
/
12.0 (MeÃ
/
Si)
1.22ꢀ0.17 (m, 12H, bridge), ꢃ
/
/
0.38 (s, 3H, SiÃCH3)
/
ꢃ22.6 (PhÃSi)
/
/
bridge), ꢃ
/
7.1 (SiÃCH3)
/
44
7.78ꢀ
bridge), ꢃ
/
6.54 (m, 37H, Flu, Ph), 1.31ꢀ
/0.27 (m, 16H,
145.7, 145.6, 145.0, 141.4, 141.3 (Cq, Flu, Ph), 135.8, 134.9,
134.5, 129.6, 127.1, 125.8, 125.1, 124.3, 120.4, 120.3 (CH,
Flu, Ph), 34.4, 34.0, 33.6, 29.1, 26.9, 23.6, 11.7, 10.8 (CH2,
ꢃ
/
11.5 (MeÃ
/
Si)
/
0.32 (s, 3H, SiÃCH3)
/
ꢃ21.0 (PhÃSi)
/
/
bridge), ꢃ
/
7.3 (SiÃCH3)
/
n.d., not determined.
a
d (ppm) in CDCl3, 25 8C.
3.12. Preparation of tetrachlorodisilane derivatives 7ꢀ
by hydrosilation reaction
/
12
was stirred for 6 h at r.t. The solvent was removed in
vacuo, the residue was suspended in Et2O and the
solution filtered over Na2SO4/SiO2. The solvent was
v-Alkenyldichloromethylsilane
mmol) and aryl or alkylsubstituted dichlorosilane (19.4
derivative
(19.4
removed in vacuo again. Yields: 90ꢀ95%. The products
were characterized by NMR spectroscopy (Table 2).
/
mmol) derivative were dissolved in 5 ml of C5H12.
Hexachloroplatinic acid (30ꢀ50 mg) was added. The
/
3.14. Preparation of the indenyl and fluorenyl substituted
mixture was stirred 40 h at r.t., then filtered over
Na2SO4 and the solvent was removed in vacuo. The
products were white, crystalline solids or slightly yellow
ligand precursors 19ꢀ28
/
Fluorenyllithium/indenyllithium (24 mmol) at r.t. was
dissolved in 100 ml of Et2O. 1,1,3,3-Tetrachloro-1-
phenyl-1,3-disila-butane (6 mmol) dissolved in 10 ml
of Et2O was added. The reaction mixture was stirred for
4 h, then filtered over Na2SO4/SiO2 and the solvent was
removed in vacuo. The crude product was dissolved in
highly viscous oils. Yields: 90ꢀ95%. The products were
characterized by NMR spectroscopy (Table 2).
/
3.13. Preparation of the cyclopentadienyl substituted
ligand precursors 13ꢀ
/
18
C5H12 and the solution crystallized at ꢃ28 8C. The
/
1,1,n,n-Tetrachloro-1-phenyl-1,n-disila-alkane
(6
products were slightly yellow powders (fluorenyl deri-
vatives) or yellow, very viscous liquids (indenyl deriva-
mmol) in 100 ml of Et2O were placed in a Schlenk
vessel and 2.1 g (24 mmol) of cyclopentadienyl sodium
(dissolved in 10 ml of THF) were added. The mixture
tives). Yields: 80ꢀ/90%. The products were characterized
by NMR spectroscopy (Table 2).

H.G. Alt, R. Ernst / Inorganica Chimica Acta 350 (2003) 1ꢀ
/
11
11
3.15. Preparation of the dinuclear metallocene complexes
29ꢀ44
References
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¨
Waymouth, Angew. Chem. 107 (1995) 1255;
General procedure: Ligand precursor (5 mmol) was
dissolved in 400 ml of Et2O. Then 12.5 ml of butyl-
lithium solution (1.6 M in C6H14; 20 mmol) was added
at r.t. The reaction mixture was stirred for 8 h.
(b) H.-H. Brintzinger, D. Fischer, R. Mulhaupt, B. Rieger, R.
¨
Waymouth, Angew. Chem., Int. Ed. Engl. 34 (1995) 1143.
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¨
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/
¨
[6] W. Spaleck, F. Kuber, B. Bachmann, C. Fritze, A. Winter, J. Mol.
¨
equimolar amount of ZrCl4 was added, then the
suspension was brought to r.t. slowly within 6 h and
was stirred for another 6 h. The solvent was removed in
vacuo, the residue was suspended in CH2Cl2 and filtered
over Na2SO4. The solvent was removed in vacuo to
almost dryness, C5H12 was added until precipitation
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started and the crude product was crystallized at ꢃ
/
28 or
ꢃ
/
78 8C. Yields: 40ꢀ80%. The complexes were charac-
/
terized by NMR spectroscopy (Table 2).
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3.16. Polymerization reactions
[13] M. Bochmann, S.J. Lancaster, M.B. Hursthouse, M. Mazid,
Organometallics 12 (1993) 4718.
An amount of 20ꢀ
complex was dissolved in 50 ml of C6H5CH3. A volume
of the solution containing 1ꢀ2 mg of the complex was
taken and activated with MAO (30% in C6H5CH3; Alꢀ
Zrꢂ2500:1).
/
25 mg of the corresponding
[14] K. Patsidis, H.G. Alt, S.J. Palackal, G.R. Hawley, Russ. Chem.
Bull. 45 (1996) 2216.
/
[15] K. Patsidis, H.G. Alt, W. Milius, S.J. Palackal, J. Organomet.
Chem. 509 (1996) 63.
/
/
[16] P. Schertl, H.G. Alt, J. Organomet. Chem. 545ꢀ
/546 (1997)
For heterogeneous polymerization reactions, un-
treated silica gel (Davison 948) was added (1 g SiO2/
mmol(Zr)) to this solution and the mixture was stirred
for 3 min. The colored precipitate contained the
activated catalyst; the supernatant solution was colorless
and clear. The heterogeneous catalyst was not separated
by filtration but applied as suspension. Both for
homogeneous and heterogeneous polymerizations the
catalyst suspension was charged to 250 ml of C5H12 and
553.
[17] H.G. Alt, M. Jung, J. Organomet. Chem. 562 (1998) 229.
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¨
Jungling, R. Mulhaupt, F. Langhauser, Organometallics 13
¨
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¨
[22] S.J. Palackal, Dissertation, Universitat Bayreuth, 1991.
¨
[23] N. Klouras, H. Kopf, Monatsh. Chem. 112 (1981) 887.
¨
filled into a 1l Buchi laboratory autoclave and thermo-
¨
stated at 60 8C. An ethylene pressure of 10 bar was
applied to the reactor and polymerization was con-
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(1985) 2539.
[25] K. Patsidis, Dissertation, Universitat Bayreuth, 1993.
ducted for 30 min at 60 (93) 8C. The obtained polymer
/
¨
[26] R. Zenk, Dissertation, Universitat Bayreuth, 1994.
¨
was dried in air for at least 60 h. The polymerization
results and the physical data of the polymers are
presented in Table 1.
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4. Supplementary material
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417.
The material is available from the authors on request.
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¨
M. Antberg, V. Dolle, E.F. Paulus, Organometallics 13 (1994)
954.
Acknowledgements
[34] J.H. Shut, Plastics World, April 1996, 41.
[35] R.L. Halterman, Chem. Rev. 92 (1992) 965.
[36] G.M. Benedikt, B.L. Goodall (Eds.), Metallocene-Catalyzed
We thank the Deutsche Forschungsgemeinschaft and
Phillips Petroleum Company (Bartlesville, OK, USA)
for financial support and the Witco Company (Bergka-
men) for the donation of methylalumoxane.
Polymers, Plastics Design Library, Norwich, NY, 1998, pp. 73ꢀ
/
80.