Amido functionalized ansa half-sandwich dichloride complexes of titanium, zirconium and hafnium with alkyl and ω-alkenyl substituents as homogeneous and self-immobilizing catalyst precursors for ethylene polymerization

Article abstract of DOI:10.1016/S0022-328X(01)00781-1

A total of 24 amido functionalized ansa half-sandwich dichloride complexes of titanium, zirconium and hafnium with cyclopentadienyl or indenyl ligands have been prepared, characterized and used for catalytic ethylene polymerization. Alkyl and ω-alkenyl substituents on the aromatic system influence the polymerization activity of the catalysts and the properties of the produced polyethylene. After activation with methylalumoxane the ω-alkenyl substituted catalysts show self-immobilization in ethylene polymerization.

Full text of DOI:10.1016/S0022-328X(01)00781-1

Journal of Organometallic Chemistry 628 (2001) 169–182
www.elsevier.nl/locate/jorganchem
Amido functionalized ansa half-sandwich dichloride complexes of
titanium, zirconium and hafnium with alkyl and v-alkenyl
substituents as homogeneous and self-immobilizing catalyst
precursors for ethylene polymerization
Helmut G. Alt *, Alexander Reb, Wolfgang Milius, Annette Weis
Laboratorium fu¨r Anorganische Chemie der Uni6ersita¨t Bayreuth, Postfach 10 12 51, D-95440 Bayreuth, Germany
Received 15 December 2000; received in revised form 26 February 2001; accepted 6 March 2001
Dedicated to Professor Max Herberhold on the occasion of his 65th birthday (August 2, 2001)
Abstract
A total of 24 amido functionalized ansa half-sandwich dichloride complexes of titanium, zirconium and hafnium with
cyclopentadienyl or indenyl ligands have been prepared, characterized and used for catalytic ethylene polymerization. Alkyl and
v-alkenyl substituents on the aromatic system influence the polymerization activity of the catalysts and the properties of the
produced polyethylene. After activation with methylalumoxane the v-alkenyl substituted catalysts show self-immobilization in
ethylene polymerization. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Group 4 metals; ansa Half-sandwich complexes; Ethylene polymerization; Self-immobilization
2. Results and discussion
1. Introduction
Since the first publication about amido functional-
ized ansa half-sandwich complexes in 1990 [1] these
compounds enjoy increasing interest as catalysts for
olefin polymerization in research and industry [2–10].
Due to their sterically open metal center they are
excellent candidates for the copolymerization of ethyl-
ene and styrene, 1-hexene or 1-octene [11,12]. In order
to investigate the effect of the catalyst structure on the
polymerization parameters and polymer properties we
functionalized the aromatic system with alkyl or v-
alkenyl groups to compare the activities of the various
catalysts. We were interested especially in the influence
of the chain length of the v-alkenyl substituents for
self-immobilization [13–15] since such amido function-
alized ansa half-sandwich complexes have not yet been
applied as heterogeneous catalysts.
2.1. Synthesis of substituted cyclopentadienyl and
indenyl deri6ati6es
In order to functionalize the ring system of cyclopen-
tadienyl compounds with alkyl or alkenyl groups the
corresponding sodium salt was treated with an alkenyl
bromide [16] in liquid ammonia [17]. Substituted in-
denyl derivatives were obtained by dissolving indene in
a mixture of diethylether and THF [18]. After addition
of one equivalent BuLi the alkyl or alkenyl bromide
was added (Scheme 1).
2.2. Synthesis of the chlorosilane deri6ati6es
Cp%SiMe2Cl and Ind%SiMe2Cl (Cp%=ꢀ-alkenyl
substituted Cp; Ind%=ꢀ-alkenyl or alkyl substituted
Ind)
To establish the silyl substituent on the functional-
ized cyclopentadiene or indene the reaction was not
carried out in an non-polar solvent as described in
* Corresponding author. Tel.: +49-921-552555; fax: +49-921-
552157.
E-mail address: helmut.alt@uni-bayreuth.de (H.G. Alt).
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)00781-1

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H.G. Alt et al. / Journal of Organometallic Chemistry 628 (2001) 169–182
silicon atom is connected with an sp2 hybridized carbon
atom [20].
The corresponding indene derivatives show a signal
for only one of the two possible isomers in the 29Si-
NMR spectrum (Fig. 2). It is possible that the steric
influence of the substituent R forces the silyl substituent
to occupy the position at the sp3 hybridized carbon
atom.
2.3. Synthesis of the ligand precursors
The synthesized chlorosilane derivatives react with a
threefold molar excess of tert-butylamine in
dichloromethane to give the products 25–36* (Scheme
2 and Fig. 3). In pentane this reaction is not efficient,
because the chlorosilane derivatives of indene do not
dissolve completely. 29Si-NMR spectroscopy is a good
tool to control the progress of the reaction.
Scheme 1. Synthesis of the cyclopentadienyl and indenyl derivatives
1–12.
2.4. Synthesis of the amido functionalized ansa
half-sandwich complexes
The amido functionalized ansa half-sandwich com-
plexes were obtained by treating the ligand precursors
with two equivalents of BuLi and then the dianion
formed with TiCl3·3THF (Fig. 4). Subsequently, PbCl2
was added as an oxidant in order to obtain the
Ti(+IV) species [21] (Scheme 3).
Fig. 1. Possible isomers of 1,3-disubstituted cyclopentadiene deriva-
tives.
2.5. Characterization by NMR spectroscopy
common procedures [19] instead of in diethylether. This
path allows a quantitative reaction.
The amido functionalized ansa half-sandwich com-
The 29Si-NMR spectroscopy plays an important role
in controlling these reactions. Every isomer of the
cyclopentadienyl derivatives shows one signal in the
29Si-NMR spectrum (Fig. 1). The signals of isomers B
and C have almost the same chemical shifts because the
1
plexes were characterized by H-, 13C- and 29Si-NMR
1
spectroscopy. The H- and 13C-NMR spectra of 45 are
1
presented in Fig. 5. The H-NMR spectrum shows two
doublets at l=7.82 and 7.74 ppm for the two protons
15 and 18. The signals at l=7.56 and 7.41 ppm are
Fig. 2. Synthesized chlorosilane derivatives 13–24*.
Scheme 2. Synthesis of the ligand precursors.

H.G. Alt et al. / Journal of Organometallic Chemistry 628 (2001) 169–182
171
Fig. 3. Synthesized ligand precursors 25–36*.
Fig. 4. Synthesized amido functionalized ansa half-sandwich complexes 37–60.
Scheme 3. Synthesis of amido functionalized ansa half-sandwich complexes.
assigned to the protons 16 and 17. These aromatic
protons have a J-ortho coupling of 8.1 Hz. The lone
ment. The singlet at l=1.49 ppm belongs to the nine
homotopic protons of the tert-butyl group. The two
diastereotopic methyl groups show their signals at l=
0.76 and 0.66 ppm.
3
proton 6 shows a singlet at l=6.44 ppm. The unsatu-
rated double bond is an ABMX2 spin system. The M
part (11) shows a multiplet at l=5.91 ppm and also
the AB part (11 and 12) at l=5.11 ppm. The three
aliphatic methylene groups 8, 9 and 10 give signals at
l=3.16, 1.93 and 2.23 ppm, respectively. This order
was confirmed by a 2D 1H,1H-COSY NMR experi-
The J-modulated 13C-NMR spectrum of 45 shows
the quaternary carbon atoms at l=138.5, 135.8, 135.0
and 96.5 ppm for the aromatic indenylidene system.
The double bond of the substituent gives signals at
l=137.5 (positive phase) and at l=115.2 ppm (nega-

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H.G. Alt et al. / Journal of Organometallic Chemistry 628 (2001) 169–182
tive phase). The three methylene groups are assigned to
the resonances at l=33.4(10), 29.1(9) and 28.4 ppm
(8). The methyl groups of the tert-butyl group and the
silicon atom show their signals at l=33.1, 3.3 and 1.0
ppm.
Every unit cell consists of six molecules: three pairs of
enantiomers. The inversion center is in the middle of
the elemental cell. The bond between the nitrogen atom
and the metal is 203.1 pm and therefore it has double
bond character. Recent crystal structures of similar
complexes show similar results [21–24]. The sum of the
bond angles around the nitrogen atom is 359.75°. This
confirms its trigonal planar surrounding; nitrogen do-
nates three electrons to the metal (Table 1).
2.6. X-ray analyses of the crystal structures of 50 and
60
The molecular structure of the hafnium complex 60
(Fig. 6) reveals that this amido functionalized ansa
half-sandwich complex exists as two enantiomers.
The preliminary molecular structure of 50 is shown
in Fig. 7. Because of thermic factors the R value of
5.4% could not be improved.
Fig. 5. (a) 250.13 MHz 1H-NMR spectrum of 45 (CDCl3, 25°C); (b) 62.9 MHz J-modulated 13C{1H}-NMR spectrum of 45 (CDCl3, 25°C).
Quaternary and CH2 carbon atoms (negative phase), CH and CH3 carbon atoms (positive phase) are in phase; S=CDCl3.

H.G. Alt et al. / Journal of Organometallic Chemistry 628 (2001) 169–182
173
Fig. 6. X-ray structure of 60. Both enantiomers are shown.
Table 1
Important bond lengths and bond angles of 60
HfꢀN
203.1(3)
237.3(13)
237.4(14)
253.8(4)
HfꢀC(2)
HfꢀC(3)
HfꢀC(4)
HfꢀC(9)
242.2(4)
238.1(4)
248.5(4)
259.2(4)
HfꢀSi
SiꢀN
SiꢀC(3)
NꢀC(15)
300.0(13)
175.1(4)
186.5(4)
149.4(6)
HfꢀCl(2)
HfꢀCl(1)
HfꢀC(1)
Cl(2)ꢀHfꢀCl(1)
NꢀSiꢀC(13)
105.6(5)
114.8(2)
HfꢀNꢀSi
NꢀSiꢀC(14)
104.8(17)
115.4(2)
NꢀSiꢀC(3)
Cl(2)ꢀHfꢀN
93.4(18)
109.9(11)
are given. In general the titanium catalysts produce a
polymer with a lower melting point and with a lower
melting enthalpy. The only exception is the
polyethylene obtained from the titanium complex 45
(R=Cꢁ5) that has a higher melting point and a higher
melting enthalpy than the corresponding zirconium
complex.
The data dealing with homogeneous ethylene poly-
merization of all synthesized complexes are shown in
Table 2.
2.7. Homogeneous ethylene polymerization
All synthesized complexes were tested for ethylene
polymerization after activation with methylalumoxane
(MAO). Fig. 8 gives an overview of the polymerization
activities of v-alkenyl substituted catalysts. Indenyli-
dene complexes have much higher activities than the
corresponding cyclopentadienylidene compounds. This
could be due to a weaker p-donor effect of the indenyl
system increasing the Lewis acidity at the central metal.
With the v-alkenyl substituted complexes of titanium
the activity increases with longer chain lengths of the
unsaturated group. A similar result has been observed
with v-alkenyl functionalized metallocene complexes
[15,25] and interpreted with the restricted mobility of
the catalyst molecule that is fixed on the backbone of
the polymer chain. Indenyl complexes of titanium and
cyclopentadienyl complexes of zirconium show the op-
posite trend. The activities decrease with longer v-
alkenyl chain lengths. At this point it is hard to predict
trends because small differences in the structure of a
catalyst, together with the reaction parameters, can
induce a strong impact on the kinetics of the polymer-
ization process. Hafnium catalysts of the amido func-
tionalized half-sandwich type generally show lower
activities in ethylene polymerization than analogous
titanium and zirconium catalysts.
In Fig. 9 the melting points (Tm) and the melting
(
enthalpies (DHm) of some of the obtained polyethylenes
Fig. 7. Preliminary X-ray structure of 50.

174
H.G. Alt et al. / Journal of Organometallic Chemistry 628 (2001) 169–182
Fig. 8. Catalyst activities in homogeneous ethylene polymerization.
2.8. Heterogeneous ethylene polymerization with
self-immobilized catalysts
1H-NMR spectra the chemical shifts refer to the resi-
dual proton signal of the solvent (l=7.24 ppm for
CHCl3-d1, l=7.15 ppm for C6H6-d6), in 13C-NMR
spectra to the solvent signal (l=77.0 ppm for CHCl3-
d1, l=128.0 ppm for C6H6-d6) and in 29Si-NMR spec-
tra to the resonance of Me4Si (external reference,
l=0.0 ppm).
Prepolymerizations. The complexes (10 mg) were dis-
solved in 75 ml C6H5CH3 and activated by adding a
250-fold molar excess of MAO (30 wt% in C6H5CH3;
Witco). Then 2 g of dried silica was added (water B1
wt%). The prepolymerization took 30 min at 0.4 bar
ethylene pressure.
Homogeneous polymerizations. The complexes were
activated by adding a 2500-fold molar excess of MAO
(30 wt%, Witco). After adding the activated complex
(ca. 2 mg) to the 1-l metal autoclave (Bu¨chi), filled with
250 ml n-C5H12, the polymerizations were performed
under an ethylene pressure of 10 bar and at a tempera-
ture of 60°C over a period of 1 h.
Heterogeneous polymerizations. A slurry of the cata-
lyst and 250 ml n-C5H12 was added to the 1-l metal
autoclave (Bu¨chi). The polymerizations were performed
under an ethylene pressure of 10 bar and at a tempera-
ture of 60°C over a period of 1 h.
The heterogeneous polymerization of ethylene was
tested with complexes 44–47. All four complexes are
substituted with an v-alkenyl chain at the indenylidene
ligand. We assume that after activation with MAO the
double bond of the v-alkenyl substituent is copolymer-
ized with ethylene in the polymer chain during the
prepolymerization step. This self-immobilization allows
the heterogenization of the catalyst system [13–15]. The
activities of the prepolymerized catalysts are given in
Fig. 10. For complex 45 an activity improvement by a
factor of 13 can be observed compared to the homoge-
neous polymerization of ethylene. Complex 46 showed
also an increase compared to the homogeneous cataly-
sis (factor of 11). Complexes 44 and 47 have lower
activities. Their v-alkenyl chain is too short or too long
for an efficient incorporation into the polymer chain
during prepolymerization. The complete data of the
polymerization of ethylene with the prepolymerized cat-
alysts are shown in Table 3.
3. Experimental
Polymer characterization. Molecular weight determi-
nations of the polyethylene (PE) samples were per-
formed using a Millipore Waters 150 C HT-GPC with
refractometric detection (RI Waters 401). The polymer
samples were dissolved in 1,2,4-trichlorobenzene (flow
rate, 1 ml min−1) and measured at 150°C.
All operations were carried out using Schlenk tech-
nique. Purified and dried Ar was used as inert gas (BTS
catalyst, molecular sieve). The solvents were dried over
Na–K alloy (Et2O, C6H5CH3, n-C5H12) and/or over
P2O5 and CaH2 (CH2Cl2).
The NMR spectra were recorded in deuterated sol-
vents at 25°C using a Bruker ARX 250 spectrometer. In
A Netzsch DSC 200 was available to determine the
thermal characteristics of the PE samples. PE (5 mg)

H.G. Alt et al. / Journal of Organometallic Chemistry 628 (2001) 169–182
175
was fused in standard aluminum pans and measured
using the following temperature program: (1) heating
phase (20°C min−1) from 50 to 170°C, isothermal
Na2SO4 and silica and the residual solvent was removed
in vacuo. Yields: 85–90%.
phase (3 min) at 170°C, cooling phase (−20°C min−1
)
3.2. Preparation of the substituted indene deri6ati6es
to 50°C; (2) heating phase (20°C min−1) from 50 to
170°C. The melting points were measured during the
second heating phase.
Indene (86 mmol) was dissolved in a mixture of 180
ml Et2O and 18 ml THF and cooled to −78°C. n-
Butyllithium (86 mmol) was added with a syringe. The
solution was allowed to warm up to room temperature
(r.t.) and stirred for 4 h. The corresponding v-alkenyl
bromide (86 mmol) was added dropwise at −78°C and
the reaction mixture was stirred for 10 h. The mixture
was hydrolyzed with 50 ml of water, filtered over
Na2SO4 and silica and the solvent was removed. Yields:
85–90%.
3.1. Preparation of substituted cyclopentadiene
deri6ati6es
In a Schlenck tube with 14.0 g (159.1 mmol) cy-
clopentadienyl sodium, 150 ml liquid NH3 was con-
densed. v-Alkenyl bromide (120.0 mmol) in 60 ml
n-C5H12 was added dropwise within 30 min. The reac-
tion mixture was stirred for 3 h. After evaporation of
the NH3, the dark brown slurry was filtered over
3.3. Preparation of 7-bromo-1-heptene
In a three-necked flask with dropping funnel, liquid
condenser and bubbler, 5 g Mg (206 mmol) in 100 ml
Et2O was placed and 24.9 g (206 mmol) allylbromide in
50 ml Et2O was added dropwise at 0°C. After stirring
for 3 h the allylmagnesiumbromide was added to 44.5 g
(206 mmol) 1,4-dibromobutane in 100 ml Et2O with a
dropping funnel within 30 min. After stirring for 4 h
the solution was hydrolyzed with 50 ml water and the
organic phase was dried over Na2SO4. After distillation
a mixture of 1,4-dibromobutane and 7-bromo-1-hep-
tene was obtained. The mixture was dissolved in 70 ml
n-C5H12 and crystallized at −78°C. The 1,4-dibro-
mobutane was precipitated and the 7-bromo-1-heptene
was collected. After removing the solvent the product
resulted in 30% yield.
3.4. General procedure for the preparation of the
substituted indene and cyclopentadiene
dimethylchlorosilane deri6ati6es 13–24*
The corresponding substituted indene or cyclopenta-
diene derivatives (80 mmol) were dissolved in 150 ml
Et2O and the solution was cooled to −78°C. n-Butyl-
Fig. 9. Melting points and melting enthalpies of polyethylenes of
indenylidene amido functionalized half-sandwich complexes from ho-
mogeneous polymerization. Cn, alkyl substituent with a chainlength
of n; Cꢁn, v-alkenyl substituent with a chainlength of n.
Fig. 10. Activities of prepolymerized catalysts.

176
H.G. Alt et al. / Journal of Organometallic Chemistry 628 (2001) 169–182
Table 2
Overview of the polymerization experiments and the polymer analyses of the homogeneous ethylene polymerizations
Complex
Activity (g) PE/(mmol) M h
GPC
DSC
Mw (g mol−1
)
Mn (g mol−1
)
HI
Tm (°C)
DHm (J g−1
)
h
a
b
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
451
695
1747
1021
566
1 461 000
101 600
14.38
127.3
127.6
121.4
127.7
129.2
129.1
136.5
136.6
141.5
138.3
n.m. e
138.8
141.5
139.2
141.9
136.7
137.5
137.1
137.4
136.9
141.3
139.9
n.m. e
139.0
153.1
154.7
175.0
130.1
147.3
167.1
99.2
98.7
126.5
101.1
53
53
60
45
51
58
34.2
34.0
43.6
34.9
Mw\1 100 000 c
1 877 000
167 700
337 700
143 100
335 700
11.19
5.27
15.36
4.49
1 780 000
2 198 000
1 508 000
547
c
(
1046
9421
3607
3324
2246
1961
2864
1396
4260
685
1542
3504
1536
2083
6384
3813
1 530
623
Mw\1 100 000
Mw\1 100 000 c
695 300
n.c. d
71 500
203 500
228 800
n.c. d
8.01
5.93
3.29
573 000
1 207 000
875 800
125.3
138.5
108.5
141.1
23.5
124.0
132.2
100.5
119.8
153.2
144.2
43.2
47.6
37.4
48.7
8.1
42.8
45.6
34.6
41.3
52.8
49.7
Mw\1 100 000 c
Mw\1 100 000 c
1 179 000
605 700
189 600
27 890
89 850
153 200
180 700
127 400
116 200
176 700
6.22
21.71
4.01
2.99
43.49
2.47
5.8
360 000
458 000
7 857 000
314 300
675 900
992 700
5.62
Mw\1 100 000 c
644 500
97 850
6.59
88.5
30.5
a The maximum of the melting peak at the second heating course of the DSC was selected as melting point.
b h=DHm/DH° with DH° =290 J g−1 [26].
m
m
c New Styragel HT6E-GPC-column; molecular weight too high.
d n.m., not measured.
e n.c., not clear (presumably multimodal resin).
lithium, 80 mmol (50 ml) (1.6 M in hexane) was added
with a syringe and the solution was stirred for 4 h and
then warmed up to r.t. The lithium salt was added to
the equimalor amount of Me2Cl2Si in 100 ml Et2O at
−78°C and stirred for 12 h. The reaction mixture was
filtered over Na2SO4 and the solvent was removed.
Yields: 80–96%.
Na2SO4. After removing the solvent the ligand precur-
sors resulted in yields between 98 and 100%.
The compounds were characterized by NMR spec-
troscopy (see Table 5).
3.6. General procedure for the preparation of the amido
functionalized ansa half-sandwich titanium complexes
37–39, 43–47, 53–56
The compounds were characterized by NMR spec-
troscopy (see Table 4).
The respective ligand precursors (18 mmol) were
dissolved in 200 ml Et2O at −78°C and 22.5 ml (36
mmol) n-butyllithium (1.6 M in hexane) was added
with a syringe. The reaction mixture was stirred for 6 h.
The dilithium salt was added to 6.64 g TiCl3·3THF in
100 ml Et2O and the solution was stirred for 10 h. The
resulting titanium(III) complex was treated with 18
mmol (4.99 g) PbCl2 and the slurry was stirred for 30
min. The solvent was removed, the residue was dis-
solved in 200 ml n-C5H12 and the solution was filtered
3.5. General procedure for the preparation of the ligand
precursors 25–36*
The respective substituted indenyl or cyclopentadi-
enyl dimethylchlorosilane derivatives (80 mmol) were
dissolved in 200 ml CH2Cl2 and 200 mmol tert-butyl-
amine was added quickly. After stirring for 4 h the
solvent was removed, the residue was dissolved in 200
ml n-C5H12 and the reaction mixture was filtered over

H.G. Alt et al. / Journal of Organometallic Chemistry 628 (2001) 169–182
177
Table 3
Overview of the polymerization experiments and the polymer analyses of the heterogeneous ethylene polymerizations with prepolymerized
catalysts
was dissolved in 200 ml n-C5H12 and the reaction
mixture was filtered over Na2SO4. The pentane was
removed until a 50 ml volume was left. The complex
was crystallized at −78°C. Yield: 25–30%.
All complexes were characterized by NMR spec-
troscopy (see Table 6).
over Na2SO4. The pentane was removed until a 50 ml
volume was left. The complex was crystallized at
−78°C. Yield: 65–95%.
The complexes were characterized by NMR spec-
troscopy (see Table 6).
3.7. General procedure for the preparation of the amido
functionalized half-sandwich complexes of zirconium
and hafnium 39–42, 48–52, 57–60
3.8. Preparation of TiCl3·3THF
THF (200 ml) and 10.0 g TiCl3 were refluxed in a 500
ml Schlenk flask for 22 h. After cooling to r.t. the blue
crystals precipitated were filtered and washed three
times with pentane. The washing was given to the
mother liquor and stored at −18°C for 24 h. The
product precipitated again in small amounts. Overall
yield: 21.96 g (92%).
The respective ligand precursors (18 mmol) were
dissolved in 200 ml Et2O at −78°C and 22.5 ml (36
mmol) n-butyllithium (1.6 M in hexane) was added
with a syringe. The reaction mixture was stirred for 6 h.
The dilithium salt was added to 18 mmol (4.19 g) ZrCl4
(or 5.72 g HfCl4) in 100 ml Et2O and the slurry was
stirred for 10 h. The solvent was removed, the residue

178
H.G. Alt et al. / Journal of Organometallic Chemistry 628 (2001) 169–182
Table 4
NMR data of the chlorosilane derivatives 13–24* a
b
Compound
1H-NMR
13C-NMR
29Si-NMR
27.5
13
7.45 (m), 7.32 (m), 7.22 (m), 6.59 (s, 1H), 6.26 (s,
Cq: 144.4, 144.1, 138.9; CH: 133.3, 132.2, 128.0,
1H), 3.43 (s, 1H), 1.86 (m, 2H), 1.56 (m, 2H), 0.52 (s, 127.5, 126.1, 125.3, 123.9, 51.6, 29.9; CH2: 17.5,
3H), 0.43 (s, 3H), 0.39 (s, 3H) 15.3; CH3: 0.7, 0.6
.
14
7.61 (d, 1H) [7.3], 7.47 (d, 1H) [7.3], 7.32 (t, 2H) [7.3], Cq: 145.0, 144.6, 143.7; CH: 127.3, 125.6, 124.4,
27.6
7.28 (t, 2H) [7.3], 6.35 (s, 1H), 3.66 (s, 1H), 2.67 (t,
2H) [7.5], 1.73 (m), 1.47 (sx, 2H) [7.35], 1.02 (t, 3H)
[7.25] 0.25 (s, 3H), 0.22 (s, 3H)
123.5, 119.4, 45.5; CH2: 30.9, 27.6, 22.9; CH3:
14.1, 0.2, −0.2
15
16
17
7.66 (d, 1H) [7.5], 7.52 (d, 1H) [7.5], 7.44 (t, 1H) [7.5], Cq: n.b.; CH: 126.3, 126.1, 124.2, 123.3, 120.5,
7.27 (t, 1H) [7.5], 6.84 (s, 1H), 3.85 (s, 1H), 2.81 (m), 48.7; CH2: 32.0, 31.8, 29.4, 22.9; CH3: 1.4, −0.4
1.82 (m), 1.57 (m), 1.10 (m), 0.58 (s, 3H), 0.31 (s, 3H)
27.6
27.7
27.7
7.66 (d, 1H) [7.5], 7.52 (d, 1H) [7.5], 7.44 (t, 1H) [7.5], Cq: 146.2, 143.7, 142.5; CH: 126.5, 126.2, 123.5,
7.27 (t, 1H) [7.5], 6.84 (s, 1H), 3.85 (s, 1H), 2.81 (m), 123.1, 120.1, 48.9; CH2: 32.9, 31.2, 29.4, 26.0, 21.9;
1.82 (m), 1.57 (m), 1.10 (m), 0.58 (s, 3H), 0.31 (s, 3H) CH3: 1.5, −0.6
8.22 (d, 1H) [7.3], 8.08 (d, 1H) [7.3], 7.96 (t, 1H) [7.3], Cq: 144.4, 143.6, 142.0; CH: 135.6, 128.5, 125.5,
7.88 (t, 1H) [7.3], 7.01 (s, 1H), 6.65 (m, 1H), 5.53 (d,
1H) [17.5], 5.77 (d, 1H) [12.5], 4.30 (s, 1H), 4.06 (m,
2H), 0.86 (s, 3H), 0.84 (s, 3H)
124.1, 123.4, 119.6, 45.6; CH2: 116.2, 32.4; CH3:
0.0, −0.3
18
19
7.61 (d, 1H) [7.5], 7.48 (d, 1H) [7.5], 7.35 (t, 1H) [7.5], Cq: 145.2, 143.9, 143.8; CH: 138.6, 128.0, 125.9,
7.27 (t, 1H) [7.5], 6.38 (s, 1H), 5.96 (m, 1H), 5.15 (d, 124.8, 123.8, 119.6, 45.9; CH2: 115.4, 33.0, 27.5;
1H) [12.5], 5.07 (d, 1H) [10], 3.67 (s, 1H), 2.77 (t, 2H) CH3: 0.4, 0.0
[7.3], 2.53 (t, 2H) [7.3], 0.24 (s, 3H), 0.22 (s, 3H)
27.6
27.5
7.59 (d, 1H) [7.5], 7.44 (d, 1H) [7.5], 7.30 (t, 1H) [7.5], Cq: 145.0, 144.5, 144.2; CH: 139.3, 127.9, 125.7,
7.22 (t, 1H) [7.5], 6.3, (s, 1H), 5.85 (m, 1H), 5.04 (d,
1H) [12.5], 5.00 (d, 1H) [10.0], 3.62 (s, 1H), 2.61 (t,
2H) [7.5], 2.17 (m, 2H), 1.79 (m, 2H), 0.21 (s, 3H),
0.16 (s, 3H)
124.3, 123.3, 118.6, 45.2; CH2: 114.1, 33.3, 29.0,
28.1, 26.8; CH3: 0.4, 0.1
20
21
7.55 (d, 1H) [7.4], 7.41 (d, 1H) [7.5], 7.28 (t 1H) [7.5], Cq: 145.1, 144.6, 143.9; CH: 139.1, 127.6, 125.8,
27.6
27.6
7.20 (t, 1H) [7.5], 6.28 (s, 1H), 5.81 (m, 1H), 5.01 (d,
1H) [12.5], 4.94 (d, 1H) [10.0], 3.60 (s, 1H), 2.60 (t,
2H) [7.5], 2.08 (m, 2H), 1.70 (m, 2H), 1.47 (m, 2H),
0.19 (s, 3H), 0.16 (s, 3H)
124.6, 123.7, 119.6, 45.8; CH2: 114.8, 33.9, 29.2,
28.3, 27.9; CH3: 0.3, 0.0
7.56 (d, 1H) [7.5], 7.44 (d, 1H) [7.5], 7.32 (t, 1H) [7.5], Cq: 145.6, 144.3, 142.8; CH: 139.0, 127.2, 125.4,
7.23 (t, 1H) [7.5], 6.31 (s, 1H), 5.82 (m, 1H), 4.98 (m, 124.2, 123.4, 119.3, 45.4; CH2: 114.3, 33.7, 29.1,
2H), 3.64 (s, 1H), 2.61 (t, 2H), 2.08 (m, 2H), 1.71 (m, 28.7, 28.3, 27.6; CH3: 0.0, −0.3
2H), 1.46 (m, 4H), 0.22 (s, 3H). 0.19 (s, 3H)
22*
23*
24*
6.75 (m, 1H), 6.71 (m), 6.61 (m), 6.52 (m), 5.82 (m,
1H), 3.22 (m, 2H), 2.57 (m, 2H), 0.83 (s, 3H), 0.65
(m, 2H)
Cq: 139.3, 134.7, 114 5; CH: 132.7, 127.6, 127.3,
114.6, 59.5, 49.4; CH2: 46.2, 33.9, 29.2; CH3: 2.3,
1.1, 0.2
28.0, 17.9, 17.2
27.9, 17.3, 16.8
28.2, 17.5, 17.0
6.89 (m, 1H), 6.77 (m), 6.60 (m), 5.84 (m, 1H), 3.23
(m, 2H), 3.09 (m, 2H), 2.67 (m, 2H), 0.91 (s, 3H),
0.60 (s, 3H)
Cq: 140.0, 135.8, 114.5; CH: 132.9, 126.8, 126.3,
114.0, 57.3, 48.9, 46.8; CH2: 34.1, 29.9, 26.6, 24.8;
CH3: 2.1, 1.8, 0.5, −0.1
6.81 (m, 1H), 6.75, (m), 6.42 (m), 5.67 (m, 1H), 3.65
(m, 2H), 3.34 (m, 2H), 2.87 (m, 2H), 2.77 (m, 2H),
0.75 (s, 3H), 0.45 (s, 3H)
Cq: 145.4, 135.5, 112.7; CH: 131.7, 124.8, 124.1,
120.3, 111.9, 59.3, 49.1; CH2: 36.9, 32.7, 29.5, 27.5,
24.2, 22.1, 19.5; CH3: 2.6, 1.9, 0.7, −0.4
a In CDCl3, at 25°C; only one isomer shown.
b Because of overlapping, the signals are not assigned to the isomers.
3.9. X-ray analysis
C16H21SiNHfCl2 (60). A yellow prism crystallized in
pentane of dimension 0.20×0.16×0.13 mm3; mono-
A Siemens P4 diffractometer (Mo–Ka radiation; u=
clinic; space group P21/c; a=14.916 (14), b=11.760 (9),
3
,
,
,
0.71073 A) with a graphite monochromator was used for
c=13.051 (13) A, i=112.29 (7)°; V=2118.2 (3) A ; Z=
4; dcalc=1.583 Mg m−3; absorption coefficient, 5.228
mm−1;F(000)=976;measured reflections, 4656; indepen-
dent reflections, 3706; goodness-of-fit; 1.026; R=2.5%.
the measurement of the reflection intensities. The struc-
ture calculation was performed with Siemens SHELXTL
PLUS (VMS).

H.G. Alt et al. / Journal of Organometallic Chemistry 628 (2001) 169–182
179
Table 5
NMR data of the ligand precursors 25–36* a
b
Compound 1H-NMR
13C-NMR
29Si-NMR
25
26
27
28
29
30
7.50 (d, 1H) [7.5], 7.37 (d, 1H) [7.5], 7.23 (t, 1H)
[7.5], 7.15 (t, 1H) [7.5], 6.32 (s, 1H), 3.45 (s, 1H),
Cq: 146.1, 144.8, 141.6, 49.6; CH: 130.5, 124.4,
123.7, 123.3, 118.9, 46.7; CH2: 30.0, 22.0; CH3: 33.8,
−1.9
2.58 (t, 2H) [7.6], 1.71 (m, 2H), 1.17 (s, 9H), 1.00 (s, 14.3, 0.0, −0.9
.
3H) [7.6], 0.04 (s, 3H), −0.05 (s, 3H)
7.59 (d, 1H) [7.2], 7.48 (d, 1H) [7.2], 7.32 (t, 1H)
[7.2], 7.3 (t, 1H) [7.2], 6.40 (s, 1H), 3.53 (s, 1H), 2.69 123.8, 123.4, 123.2, 119.0; CH2: 31.1, 27.6, 22.9;
(t, 2H) [7.4], 1.76 (m, 2H), 1.54 (m, 2H), 1.27 (s,
9H), 1.05 (t, 3H) [7.3], 0.05 (s, 3H), −0.03 (s, 3H)
Cq: 146.2, 144.9, 141.8, 49.6; CH: 130.4, 124.5,
−1.9
−1.9
−2.0
−1.9
−1.9
CH3: 34.0, 14.1, 0.1, −0.7
7.59 (d, 1H) [7.5], 7.48 (d, 1H) [7.5], 7.32 (t, 1H)
[7.5], 7.23 (t, 1H) [7.5], 6.40 (s, 1H), 3.53 (s, 1H),
2.69 (t, 2H) [7.4], 1.76 (m, 2H) 1.54 (m, 2H), 1.05 (t, CH3: 34.0, 14.1, 0.1, −0.7
3H) [7.4], 0.05 (s, 3H), −0.03 (s, 3H)
Cq: 146.2, 144.9, 141.8, 49.6; CH: 130.4, 124.4,
123.8, 123.4, 123.2, 119.0, 46.7; CH2 31.1, 27.6, 22.9;
7.49 (d, 1H) [7.3], 7.36 (d, 1H), [7.3], 7.21 (t, 1H)
[7.3], 7.16 (t, 1H) [7.3], 6.30 (s, 1H), 3.44 (s, 1H),
2.58 (t, 2H) [7.4], 1.66 (m, 2H), 1.32 (m, 4H), 1.17 (s, 27.8, 22.7; CH3: 33.8, 14.2, 0.0, −0.9
9H), 0.88 (m, 2H), −0.08 (s, 3H), −0.15 (s, 3H)
Cq: 145.1, 144.2, 141.8, 46.7; CH: 130.3, 124.4,
123.7, 123.3, 123.1, 118.9; CH2: 31.8, 29.5, 28.8,
8.19 (d, 1H) [7.5], 8.07 (d, 1H) [7.5], 7.92 (t, 1H)
[7.5], 7.85 (t, 1H) [7.5], 7.05 (s, 1H), 6.70, (m, 1H),
5.78 (m, 2H), 4.17 (s, 1H), 4.05 (d, 2H) [5.3], 1.87 (s, CH3: 34.1, 0.2, −0.6
Cq: 146.3, 143.1, 139.5, 49.8; CH: 136.6, 131.9,
124.6, 123.7, 123.3, 119.4, 47.2; CH2: 116.0, 32.8;
9H), 0.64 (s, 3H), 0.58 (s, 3H)
7.73 (d, 1H) [7.3], 7.60 (d, 1H) [7.3.], 7.46 (t, 1H)
[7.3], 7.8 (t, 1H) [7.3], 6.57 (s, 1H), 6.14 (ddt, 1H),
5.31 (dd, 1H), 5.25 (dd, 1H), 3.67 (s, 1H), 2.93 (m,
2H), 2.70 (m, 2H), 1.39 (s, 9H), 0.19 (s, 3H), 0.12 (s,
3H)
Cq: 146.5, 145.1, 141.3, 50.0; CH: 139.0, 131.0,
125.0, 124.0, 123.6, 119.3, 47.2; CH2: 115.2, 33.4,
27.8; CH3: 34.3, 0.6, −0.3
[1J(29Si,13C)=12
Hz]
31
32
33
7.59 (d, 1H) [7.3], 7.46 (d, 1H) [7.3], 7.29 (t, 1H)
[7.3], 7.24 (t, 1H) [7.3], 6.41 (s, 1H), 5.94 (ddt, 1H),
5.09 (dd, 1H), 5.05 (dd, 1H), 3.55 (s, 1H), 2.70 (t,
2H) [7.5], 2.24 (m, 2H), 1.86 (m, 2H), 1.27 (s, 9H),
0.87 (s, 3H), 0.79 (s, 3H)
Cq: 146.0, 144.1, 141.3, 50.1; CH: 138.7, 130.5,
124.3, 123.4, 123.0, 118.8, 46.7; CH2: 114.7, 33.7,
28.0, 27.1; CH3: 33.8, 0.0, −0.9
−2.0
7.59 (d, 1H) [7.3], 7.46 (d, 1H) [7.3], 7.31 (t, 1H),
[7.3], 7.23 (t, 1H) [7.3], 6.41 (s, 1H), 5.95 (ddt, 1H),
5.09 (dd, 1H), 5.03 (dd, 1H), 3.53 (s, 1H), 2.69 (t,
2H) [7.6], 2.20 (m, 2H), 1.76 (m, 2H), 1.61 (m, 2H),
1.27 (s, 9H), 0.05 (s, 3H), −0.04 (s, 3H)
Cq: n. b. (DEPT); CH: 145.0, 137.1, 131.0, 129.8,
128.6, 124.9, 52.7; CH2: 121.1, 39.9, 36.0, 35.0, 34.1;
CH3: 40.1, 3.0, 2.6
−1.9
7.53 (d, 1H) [7.7], 7.40 (d, 1H) [7.7], 7.26 (t, 1H)
[7.7], 7.18 (t, 1H) [7.7], 6.34 (s, 1H), 6.87 (m, 1H),
4.98 (m, 2H), 3.48 (s, 1H), 2.62 (m, 2H), 2.10 (m,
2H), 1.71 (m, 2H), 1.45 (m, 4H), 1.24 (s, 9H), −0.02
(s, 3H), −0.10 (s, 3H)
Cq: 146.0, 144.7, 141.6, 49.3; CH: 141.6, 130.3,
124.3, 123.3, 123.0, 118.8, 46.6; CH2: 33.8, 29.2,
28.8, 28.6, 27.7; CH3: 33.8, −0.1, −1.0
−2.0
34*
35*
36*
7.34 (m), 6.72 (m), 6.68 (m), 6.31 (m), 5.60 (m), 2.97 Cq: 149.5, 144.4, 141.8, 139.5, 54.7, 49.7, 43.2; CH:
(m), 1.93 (m), 1.79 (m), 1.03 (s), 0.76 (s), 0.62 (s)
−3.7, −14.3,
136.9, 135.7, 132.5, 127.9, 124.5, 123.9, 120.5, 116.7; −14.5
CH2: 113.1, 34.6, 28.9, 26.7, 23.5; CH3: 30.7, 3.6,
−0.1
7.41 (m), 6.82 (m), 6.75 (m), 6.35 (m), 5.63 (m), 3.06 Cq: 154.5, 149.8, 145.7, 53.2, 49.3, 44.6; CH: 138.4,
(m), 2.73 (m), 1.88 (s), 1.83 (s), 0.91 (s), 0.78 (s), 0.66 138.1, 133.7, 130.3, 127.3, 126.8, 125.9, 114.6, 114.4; −14.7
−3.6, −14.2,
(s)
CH2: 114.5, 33.8, 32.8, 29.1, 27.2, 26.5; CH3: 30.3,
3.5, −0.2
7.43 (m), 7.01 (m), 6.76 (m), 6.27 (m), 5.44 (m), 2.89 Cq:145.9, 145.0, 142.9, 139.3, 53.6, 49.9, 45.1; CH:
−3.5, −14.4,
134.7, 132.7, 131.9, 130.8, 127.9, 127.8, 125.3, 114.9; −15.0
CH2: 114.8, 34.2, 29.2; CH3: 30.1, 2.1, 0.4
(m), 2.23 (m), 1.95 (m), 1.76 (m), 1.54 (m), 0.98 (s),
0.76 (s), 0.69 (s).
a In CDCl3 at 25°C; only one isomer shown.
b Because of overlapping, the signals are not assigned to the isomers.

180
H.G. Alt et al. / Journal of Organometallic Chemistry 628 (2001) 169–182
Table 6
NMR data of the amido functionalized ansa half-sandwich complexes 37–60 a
Complex
1H-NMR
13C-NMR
29Si-NMR
37
6.53 (m, 1H), 6.10 (m, 1H), 5.93 (m, 1H), 5.66 (m, 2H), Cq: 146.5, 108.7, 64.1; CH: 137.9, 125.8, 125.6, 125.1; −19.4
4.95 (m, 1H), 2.67 (m, 2H), 2.15 (m, 2H), 1.38 (s, 9H),
CH2: 115.9, 34.2, 30.3; CH3: 32.6, 0.2, 0.0
0.25 (s, 3H), 0.23 (s, 3H)
.
38
39
40
41
42
43
6.80 (m, 1H), 6.38 (m, 1H), 6.22 (m, 1H), 5.93 (m, 2H), Cq: 145.7, 109.1, 63.2; CH: 137.8, 126.2, 125.0, 124.9; −19.7
5.23 (m, 1H), 2.84 (m, 2H), 2.15 (m, 2H), 1.73 (m, 2H), CH2: 114.8, 33.4, 29.8; CH3: 32.0, 0.2, 0.0
1.66 (s, 9H), 0.50 (s, 3H), 0.49 (s, 3H)
6.56 (m, 1H), 6.12 (m, 1H), 5.98 (m, 1H), 5.68 (m, 2H), Cq: 145.6, 110.0, 63.8; CH: 126.8, 125.8, 125.5; CH2:
−19.5
−20.3
−20.4
−20.4
−20.0
4.95 (m, 1H), 2.59 (m, 2H), 1.90 (m, 2H), 1.56 (m, 2H)
1.43 (m, 2H), 1.27 (s, 9H), 0.25 (s, 3H), 0.22 (s, 3H)
137.8, 114.8, 33.4, 29.8; CH3: 32.0, 0.2, 0.0
6.38 (m, 1H), 6.13 (m, 1H), 5.98 (m, 1H), 5.66 (m, 2H), Cq: 140.1, 108.8, 57.8; CH: 122.4, 121.8, 120.1; CH2:
4.95 (m, 1H), 2.64 (m, 2H), 2.16 (m, 2H), 1.30 (s, 9H),
0.29 (s, 3H), 0.27 (s, 3H)
137.5, 115.8, 108.8, 34.6, 29.2; CH3: 32.7, 0.9, 0.7
6.36 (m, 1H), 6.32 (m, 1H), 6.26 (m, 1H), 5.98 (m, 2H), Cq: 145.3, 108.5, 63.7; CH: 125.8, 125.3, 123.7; CH2:
5.14 (m, 1H), 2.81 (m, 2H), 2.12 (m, 2H), 1.81 (m, 2H), 136.9, 114.8, 33.8, 29.8, 28.9; CH3: 32.0, 1.2, 0.5
1.63 (s, 9H), 0.42 (s, 3H), 0.45 (s, 3H)
6.33 (m, 1H), 6.16 (m, 1H), 6.02 (m, 1H), 5.69 (m, 2H), Cq: 145.1, 109.0, 57.8; CH: 122.6, 121.8, 120.3; CH2:
4.97 (m, 1H), 2.52 (m, 2H), 1.90 (m, 2H), 1.57 (m, 2H)
1.37 (m, 2H), 1.32 (s, 9H), 0.30 (s, 3H), 0.28 (s, 3H)
138.9, 115.0, 33.9, 30.4, 29.9, 29.4; CH3: 33.0, 1.1, 0.9
7.23 (d, 1H) [8.5], 7.13 (d, 1H) [8.5], 7.01 (t, 1H) [8.5],
6.87 (t, 1H) [8.5], 6.22 (s, 1H), 5.67 (m, 1H), 4.78 (m,
2H), 3.75 (m, 2H), 1.27 (s, 9H), 0.87 (s, 3H), 0.43 (s,
3H)
Cq: 136.1, 134.4, 132.1, 97.5, 62.5; CH: 135.4, 128.6,
128.1, 127.4, 124.7; CH2: 116.6, 33.6; CH3: 32.2, 2.9,
0.6
44
45
46
47
7.61 (d, 1H) [8.5], 7.74 (d, 1H) [8.5], 7.08 (t, 1H) [8.5],
7.01 (t, 1H) [8.5], 6.26 (s, 1H), 5.69 (m, 1H), 4.95 (m,
2H), 2.92 (m, 2H), 2.26 (m, 2H), 1.23 (s, 9H), 0.60 (s,
3H), 0.40 (s, 3H)
Cq: 137.5, 136.0, 135.2, 96.7, 62.8; CH: 137.5, 128.8,
124.8, 125.6, 122.9; CH2: 115.4, 34.6, 28.8; CH3: 32.8
3.2, 0.8
−19.9
−20.4
−20.2
−20.2
7.82 (d, 1H) [8.1], 7.74 (d, 1H) [8.1], 7.56 (t, 1H) [8.1],
7.41 (t, 1H) [8.1], 6.44 (s, 1H), 5.91 (m, 1H), 5.11 (m,
2H), 3.19 (m, 2H), 2.23 (m, 2H), 1.93 (m, 2H), 1.49 (s,
9H), 0.76 (s, 3H), 0.66 (s, 3H)
Cq: 138.5, 135.8, 135.0, 115.2, 63; CH: 137.9, 128.6,
128.1, 127.5, 126.9, 123.2; CH2: 115.2, 33.4, 29.1, 28.4;
CH3: 33.1, 3.3, 1.0
7.60 (d, 1H) [8.5], 7.36 (d, 1H) [8.5], 7.15 (t, 1H) [8.5],
6.98 (t, 1H) [8.5], 6.24 (s, 1H), 5.69 (m, 1H), 4.96 (m,
2H), 2.89 (m, 2H), 1.89 (m, 2H), 1.55 (m, 2H), 1.32 (m, 29.0; CH3: 32.5, 3.3, 0.9
2H), 1.31 (s, 9H), 0.56 (s, 3H), 0.37 (s, 3H)
Cq: 136.7, 135.7, 131.3, 92.6, 63.1; CH: 138.7, 128.8,
128.4, 127.6, 125.7, 124.9; CH2: 114.8, 33.8, 29.8, 29.3,
7.66 (d, 1H) [8.5], 7.45 (d, 1H) [8.5], 7.22 (t, 1H) [8.5],
7.07 (t, 1H) [8.5], 6.34 (s, 1H), 5.79 (m, 1H), 5.06 (m,
Cq: 138.5, 135.8, 135.0, 96.4, 62.5; CH: 138.6 128.5,
127.3, 126.9, 125.7, 124.6; CH2: 114.4, 33.7, 29.8, 29.1,
2H), 3.03 (m, 2H), 1.98 (m, 2H), 1.52 (m, 2H), 1.40 (m, 28.9, 28.6; CH3: 32.2, 3.0, 0.6
2H), 1.36 (s, 9H), 1.31 (m, 2H), 0.59 (s, 3H), 0.46 (s,
3H)
48
49
50
51
7.36 (d, 1H) [8.5], 7.41 (d, 1H) [8.5], 7.03 (t, 1H) [8.5],
6.97 (t, 1H) [8.5], 6.28 (s, 1H), 5.97 (m, 1H), 4.98 (m,
2H), 3.68 (m, 2H), 1.22 (s, 9H), 0.59 (s, 3H), 0.37 (s,
3H)
Cq: 136.1, 134.2, 132.5, 90.9, 57.4; CH: 135.5, 127.6,
126.0, 125.6, 124.0; CH2: 116.4, 32.8; CH3: 32.4, 3.6,
1.6
−20.4
−20.5
−20.5
−20.5
7.61 (d, 1H) [8.5], 7.74 (d, 1H) [8.5], 7.08 (t, 1H) [8.5],
7.01 (t, 1H) [8.5], 6.26 (s, 1H), 5.69 (m, 1H), 4.95 (m,
2H), 2.92 (m, 2H), 2.26 (m, 2H), 1.23 (s, 9H), 0.60 (s,
3H), 0.40 (s, 3H)
Cq: 136.3, 134.2, 131.8, 90.6, 57.0; CH: 137.5, 127.6,
127.3, 125.6, 124.1; CH2: 115.7, 34.4, 27.7; CH3: 33.0
3.9, 1.8
7.64 (d, 1H) [8.5], 7.35 (d, 1H) [8.5], 7.06 (t, 1H) [8.5],
6.98 (t, 1H) [8.5], 6.28 (s, 1H), 5.89 (m, 1H), 5.00 (m,
2H), 2.78 (m, 2H), 1.94 (m, 2H), 1.57 (m, 2H), 1.23 (s,
9H), 0.60 (s, 3H), 0.39 (s, 3H)
Cq: 136.2, 134.3, 131.1, 95.6, 57.3; CH: 138.2, 127.9,
127.4, 125.9, 124.1, 124.0; CH2: 115.3, 33.7, 29.7, 27.7;
CH3: 33.0, 3.9, 1.8
7.48 (d, 1H) [8.5], 7.26 (d, 1H) [8.5], 6.94 (t, 1H) [8.5],
6.84 (t, 1H) [8.5], 6.17 (s, 1H), 5.69 (m, 1H), 4.83 (m,
Cq: 136.2, 134.7, 131.9, 92.6, 62.3; CH: 138.6, 127.9,
127.7, 126.0, 125.7, 124.0; CH2: 114.8, 33.7, 29.9, 28.9,
2H), 2.74 (m, 2H), 1.78 (m, 2H), 1.38 (m, 2H), 1.14 (m, 28.1; CH3: 33.1, 4.0, 1.9
2H), 1.10 (s, 9H), 0.46 (s, 3H), 0.25 (s, 3H)

H.G. Alt et al. / Journal of Organometallic Chemistry 628 (2001) 169–182
181
Table 6 (Continued)
Complex
1H-NMR
13C-NMR
29Si-NMR
52
7.63 (d, 1H) [8.5], 7.36 (d, 1H) [8.5], 7.07 (t, 1H) [8.5],
Cq: 137.8, 126.6, 126.0, 91.3, 58.9; CH: 137.8, 126.6,
−20.8
6.96 (t, 1H) [8.5], 6.20 (s, 1H), 5.70 (m, 1H), 4.96 (m, 2H),127.7, 126.0, 125.7, 124.0; CH2: 114.1, 32.4, 27.4, 28.2,
2.91 (m, 2H), 1.92 (m, 2H), 1.30 (m, 2H), 1.24 (m, 2H), 27.4; CH3: 33.5, 4.9, 1.8
1.22 (s, 9H), 0.64 (s, 3H), 0.43 (s, 3H)
.
53
54
55
56
57
58
59
60
7.57 (d, 1H) [8.5], 7.33 (d, 1H), [8.5], 7.12 (t, 1H) [8.5],
7.02 (t, 1H) [8.5], 6.21 (s, 1H), 2.99 (m, 2H), 1.52 (t, 2H) 124.9, 124.6, 123.7; CH2: 31.1, 22.7; CH3: 32.2, 14.0,
[7.5], 1.31 (s, 9H), 0.89 (t, 3H) [7.5], 0.57 (s, 3H), 0.38 (s, 3.0, 0.7
3H)
Cq: 138.9, 137.3, 127.3, 97.0, 58.6; CH: 128.5, 127.4,
−20.2
7.60 (d, 1H) [8.5], 7.36 (d, 1H) [8.5], 7.15 (t, 1H) [8.5],
Cq: 138.8, 137.1, 135.4, 99.9, 63.1; CH: 128.1, 127.2,
−20.2
7.05 (t, 1H) [8.5], 6.24 (s, 1H), 3.02 (m, 2H), 1.49 (m, 2H),126.2, 125.0, 118.1; CH2: 33.4, 29.9, 23.3; CH3: 33.2,
1.31 (s, 9H), 1.21 (m, 2H), 0.81 (t, 3H) [7.3], 0.58 (s, 3H), 14.2, 4.1, 2.1
0.39 (s, 3H)
7.65 (d, 1H) [8.5], 7.43 (d, 1H) [8.5], 7.22 (t, 1H) [8.5],
Cq: 138.5, 136.7, 134.8, 100.3, 62.2; CH: 128.7, 126.8, −20.2
7.09 (t, 1H) [8.5], 6.31 (s, 1H), 3.30 (m, 2H), 3.08 (m, 2H),126.1, 124.6, 113.9; CH2: 33.4, 29.9, 25.4, 23.3; CH3:
1.56 (m, 2H), 1.38 (s, 9H), 1.12 (m, 2H), 0.90 (t, 3H) [7.3],33.7, 12.3, 3.7, 2.4
0.64 (s, 3H), 0.45 (s, 3H)
7.69 (d, 1H) [8.5], 7.34 (d, 1H) [8.5], 7.11 (t, 1H) [8.5],
7.09 (t, 1H) [8.5], 6.22 (s, 1H), 3.33 (m, 2H), 3.18 (m, 2H),125.4, 123.1, 114.3; CH2: 32.9, 28.7, 24.2, 22.9, 21.3;
2.88 (m, 2H), 1.59 (m, 2H), 1.43 (s, 9H), 1.11 (m, 2H),
0.88 (t, 3H) [7.3], 0.58 (s, 3H), 0.39 (s, 3H)
Cq: 137.6, 136.7, 135.8, 98.9, 64.1; CH: 128.6, 126.2,
−20.2
−20.5
CH3: 33.1, 11.7, 3.3, 2.1
7.70 (d, 1H) [8.5], 7.41 (d, 1H), [8.5], 7.10 (t, 1H) [8.5],
7.01 (t, 1H) [8.5], 6.30 (s, 1H), 2.99 (m, 2H), 1.60 (t, 2H) 125.6, 125.5, 123.9; CH2: 30.0, 23.5; CH3: 32.8, 13.8,
[7.5], 1.31 (s, 9H), 0.90 (t, 3H) [7.5], 0.75 (s, 3H), 0.52 (s, 3.7, 1.6
3H)
Cq: 139.1, 134.9, 128.9, 92.0, 56.8; CH: 128.2, 127.3,
7.56 (d, 1H) [8.5], 7.28 (d, 1H) [8.5], 7.13 (t, 1H) [8.5],
Cq: 142.2, 139.6, 135.8, 100.7, 59.5; CH: 127.1, 126.8, −20.5
6.98 (t, 1H) [8.5], 6.21 (s, 1H), 2.98 (m, 2H), 1.42 (m, 2H),126.2, 124.7, 117.9; CH2: 32.6, 28.9, 23.1; CH3: 32.6,
1.41 (s, 9H), 1.26 (m, 2H), 0.87 (t, 3H) [7.3], 0.67 (s, 3H), 13.9, 3.8, 2.0
0.29 (s, 3H)
7.67 (d, 1H) [8.5], 7.55 (d, 1H) [8.5], 7.14 (t, 1H) [8.5],
Cq: 142.1, 141.7, 140.2, 89.9, 55.2; CH: 127.9, 127.1,
−20.5
−20.8
7.02 (t, 1H) [8.5], 6.43 (s, 1H), 2.70 (m, 2H), 3.12 (m, 2H),125.1, 123.8, 119.3; CH2: 33.1, 29.2, 24.2, 22.7; CH3:
1.55 (m, 2H), 1.27 (s, 9H), 1.12 (m, 2H), 0.94 (t, 3H) [7.3],33.8, 14.2, 4.0, 1.9
0.45 (s, 3H), 0.21 (s, 3H)
7.74 (d, 1H) [8.5], 7.45 (d, 1H) [8.5], 7.17 (t, 1H) [8.5],
Cq: 139.9, 133.6, 127.0, 89.8, 55.3; CH: 127.3, 126.8,
7.10 (t, 1H) [8.5], 6.31 (s, 1H), 2.93 (m, 2H), 1.64 (t, 2H) 125.6, 124.5, 123.7; CH2: 29.8, 23.7; CH3: 33.6, 13.8,
[7.5], 1.34 (s, 9H), 0.93 (t, 3H) [7.5], 0.75 (s, 3H), 0.54 (s, 4.0, 1.9
3H)
a In C6H6-d6 at 25°C.
[5] Exxon Chemical Co., US Patent 5,026,798, 1991.
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3356.
Acknowledgements
We thank Phillips Petroleum Company (Bartlesville,
OK, USA) for the financial support and Witco Com-
pany for a donation of methylaluminoxane.
[8] J.C. Stevens, F.J. Timmers, D.R. Wilson, G.F. Schmidt, N.P.
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