New indenyl titanium catalysts for syndiospecific styrene polymerizations

Article abstract of DOI:10.1016/S0022-328X(99)00095-9

A series of multi-methyl-substituted indenes as well as allylindene, n-propylindene, n-but-1-enylindene, and n-butylindene have been prepared in good yields. The substituted indenes were converted into trimethylsilyl derivatives via reactions of intermediate organolithium complexes with chlorotrimethylsilane. The corresponding titanium complexes were synthesized in excellent yields from reactions of the trimethylsilyl derivatives with TiCl₄. The titanium complexes were evaluated as styrene polymerization catalysts in toluene solution when activated by methylaluminoxane. In general, catalytic activities decreased with each additional methyl substituent. Syndiospecificities were very high (90-95%).

Full text of DOI:10.1016/S0022-328X(99)00095-9

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 583 (1999) 11–27
New indenyl titanium catalysts for syndiospecific styrene
polymerizationsꢀ
Thomas E. Ready, James C.W. Chien, Marvin D. Rausch *
Department of Chemistry, Lederie Graduate Research Center, Uni6ersity of Massachusetts, Amherst, MA 01003, USA
Received 11 May 1998; received in revised form 8 August 1998
Abstract
A series of multi-methyl-substituted indenes as well as allylindene, n-propylindene, n-but-1-enylindene, and n-butylindene have
been prepared in good yields. The substituted indenes were converted into trimethylsilyl derivatives via reactions of intermediate
organolithium complexes with chlorotrimethylsilane. The corresponding titanium complexes were synthesized in excellent yields
from reactions of the trimethylsilyl derivatives with TiCl4. The titanium complexes were evaluated as styrene polymerization
catalysts in toluene solution when activated by methylaluminoxane. In general, catalytic activities decreased with each additional
methyl substituent. Syndiospecificities were very high (90–95%). © 1999 Elsevier Science S.A. All rights reserved.
Keywords: Titanium; Lithium; Ion-pairs; Indenyl complexes; Styrene; Polymerization
1. Introduction
catalytic activity and in general increase syndiospecific-
ity. On the other hand, bulky substituents or Lewis
base groups on the indenyl ligand were found to reduce
catalytic activity dramatically.
In order to further investigate these effects, we have
synthesized a series of multi-methyl-substituted indenyl-
trichlorotitanium complexes and compared their rela-
tive catalytic activities toward styrene when activated
with MAO.
h5-(Cyclopentadienyl)trichlorotitanium
(CpTiCl3)
and its analogs have been demonstrated to be effective
syndiospecific catalyst precursors for the Ziegler–Natta
polymerization of styrene when activated by methylalu-
minoxane (MAO) [1]. Several studies have demon-
strated that substitution of the h5-cyclopentadienyl or
h5-indenyl ligands in metallocene and ansa-metallocene
Ziegler–Natta catalysts can influence both the catalyst
activity and polymer stereoregularity [2]. We have pre-
viously reported [3] that replacing the cyclopentadienyl
ligand with an indenyl (Ind) ligand increases the cata-
lytic activity, stereospecificity, and thermal stability of
the catalyst at elevated temperatures, and that electron-
releasing substituents on the indenyl ligand can increase
2. Results and discussion
2.1. Synthesis of catalyst precursors
2.1.1. Synthesis of multi-methylated indenes
Indenes with more than one methyl group were syn-
thesized from the corresponding highly methylated in-
danones using modifications of literature procedures
[4]. The highly methylated indanones were prepared by
reactions of the appropriate combination of acid chlo-
ride (acryloyl chloride, crotonoyl chloride, or tigloyl
chloride) and either benzene or methyl-substituted ben-
zenes (p-xylene or 1,2,3,4-tetramethylbenzene) in the
presence of AlCl3 (Eq. 1).
ꢀ Dedicated to Professor Alberto Ceccon on his 65th birthday in
recognition of his outstanding contributions to Organometallic
Chemistry.
* Corresponding author. Tel.: +1-413-5452291; fax: +1-413-
5454490.
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00095-9

12
T.E. Ready et al. / Journal of Organometallic Chemistry 583 (1999) 11–27
The highly methylated indanones were converted to
which isomer was isolated, consistent with the results of
others [5]. When the reactions between the indenyl-
lithium and the alkyl or alkenyl halides (CH3(CH2)2Br,
CH2ꢀCHCH2Br, and CH3(CH2)3Br) occured in hexane
or ethyl ether solution, the 1-position alkyl or alkenyl-
substituted indene isomer was isolated (Eq. 3). When
this type of substitution reaction was carried out with
CH2ꢀCHCH2CH2Br in THF solution, the 3-position
alkyl-substituted indene isomer was isolated (Eq. 4).
When an indenyl anion substitutes on an organic
substrate, the 1-alkylindene isomer must be formed
initially. The question that arises is, why do these
substitution reactions lead via tautomerization to the
3-alkylindene isomer in THF but not to any apprecia-
ble extent in ethyl ether or hexane?
indanols either by reaction with methyllithium or by
reduction using LiAlH4 followed by hydrolysis. The
indanols were then dehydrated using p-toluenesulfonic
acid in refluxing toluene to produce the desired multi-
methylated indenes (I–VII, Eq. 2).
(1)
Several explanations are possible for the isomeriza-
tion of 1-alkylindenes to 3-alkylindenes in THF but not
in ethyl ether or hexane. They are the result of solvent
stabilization of the transition state ion-pair [7].
In THF, the indenyl–lithium ion pair is apparently
solvent separated to a much greater degree than the
same ion pair in ethyl ether or alkane solvents [5d, 8].
The 1H-NMR spectrum of indenyllithium in THF
shows that the protons at the 1- and 3-positions are
magnetically equivalent [9], consistent with the idea of a
solvent separated ion pair. (note: the idea of a THF
solvent separated ion pair is disputed [10].) Thus, once
any alkyl-substituted indene is formed, another THF
solvated indenyl anion can act as a base catalyst and is
able to isomerize the substituted indene easily to the
more thermodynamically stable 3-isomer [11]. The ex-
tended reaction times used in this process would osten-
sibly allow for near total conversion to the more stable
isomer. In hexane or ethyl ether, however, indenyl-
lithium forms a contact ion pair which is incapable,
either due to sterics or by virtue of its substantially
reduced solubility in these solvents, to act as a base.
Thus, very little isomerization of the 1-alkylindene
formed to 3-alkylindene occurs in these solvents.
(2)
2.1.2. Synthesis of mono alkyl-substituted indenes
Mono-alkylindenes substituted at the 1- or 3-position
were synthesized via reactions of indenyllithium with
alkyl or alkenyl halides using hexane, ethyl ether, or
tetrahydrofuran as a solvent by modifications to the
literature methods [5] (Eqs. 3 and 4).
2.1.3. Synthesis of trimethylsilylindenes
Trimethylsilylindenes were prepared in high yields via
reactions of indenyllithium intermediates with chloro-
trimethylsilane using modifications of literature proce-
dures [12]. The reactions of chlorotrimethylsilane with
the anions of highly methylated indenes were carried
out in THF to insure completeness, since it is much
more difficult to lithiate these ligands than mono-alky-
lated indenes (Eq. 5). Reactions of 1- or 3-alkyl substi-
tuted indenyllithium intermediates with chloro-
trimethylsilane in hexane formed the corresponding
1-trimethylsilyl-3-alkylindene (Eq. 6). The formation of
this isomer under these conditions is consistent with the
action of strong thermodynamic driving forces: (1) the
alkyl substituent prefers to be in the 3-position, stabiliz-
ing the 5-membered ring double bond; and (2) the
trimethylsilyl group prefers to be in the 1-position to
alleviate co-planar peri-steric interactions.
(3)
(4)
Substitution at the 2-position does not occur via this
method probably because substitution at the less elec-
tron dense C-2 carbon [6] may require the formation of
a high energy isoindene intermediate.
We reported previously [3a] that the particular sol-
vent used in these substitution reactions controlled

T.E. Ready et al. / Journal of Organometallic Chemistry 583 (1999) 11–27
13
(5)
(8)
It was hoped that the synthesis of indenyltrimethyl-
titanium (13) would lead to catalyst precursors which
could be activated with trityl tetrakis-(pen-
tafluorophenyl)borate [16]. Indenyltrimethyltitanium
was synthesized via reaction of indenyltrichlorotitanium
with three equivalents of methyllithium (Eq. 9). Al-
1
though a suitable H-NMR spectrum of (13) was ob-
tained, a complementary analytical analysis was not
obtained due to the thermal instability of the com-
pound. A sequential methylation of IndTiCl3 was also
tried, and indenyldichloromethyltitanium (14) was suc-
cessfully isolated (Eq. 10). However, attempts to con-
vert 14 to higher methylated analogues failed.
(6)
2.1.4. Synthesis of mono-indenyl titanium complexes
h5-Indenyltrichlorotitanium complexes (1–7, 9–12)
were synthesized by adapting the literature procedures
for the synthesis of CpTiCl3 [13a] and Cp*TiCl3 (8)
[13b]. The trimethylsilylindene derivatives were reacted
with TiCl4 in methylene chloride at ambient tempera-
ture to give the corresponding mono-indenyl titanium
complexes in excellent yields (Eqs. 7 and 8). The tita-
nium complexes in this study are appreciably more
soluble in organic solvents than similar complexes syn-
thesized previously. Hence, they were best purified by
crystallization from pentane. In general, the
organometallic complexes reported here decompose
within 2 h in the solid state, and within an hour in
solution, when they are exposed to normal atmosphere.
While this work was in progress [14], the synthesis and
X-ray structure for h5-heptamethylindenyltrichlorotita-
nium [4f] as well as the synthesis and s-PS activity for
1,3-dimethylindenyltrichlorotitanium [15] were reported
in the literature.
(9)
(10)
The mixed ring complex h5-indenyl-h7-cyclohepta-
trienyltitanium (15) was synthesized by reacting
IndTiCl3 with Mg turnings in the presence of cyclohep-
tatriene under modified literature conditions previously
described [17] for CpTi(C7H7) (Eq. 11).
(11)
2.2. Polymerization results
Our previous study [3a] indicated that differences in
activities between the catalysts containing the same
(7)

14
T.E. Ready et al. / Journal of Organometallic Chemistry 583 (1999) 11–27
ancillary ligands are, by and large, not attributable to
differences in their ability to be activated by MAO
solution. Thus, preactivation or aging of catalysts was
not performed in this work.
Comparative polymerization results at 50, 75, and
100°C for Cp*TiCl3 (8) and the various indenyl
titanium catalysts are reported in Table 1. Plots of
log(styrene activity) versus T−p 1 for the various
catalysts are shown in Figs. 1, 2 and 3.
XPS studies [24] suggest that the electron binding
energy on the titanium center could be lowered by as
much as 0.1 eV per methyl substituent on the h5-ring of
the cyclopentadienyl ligand and that much again by the
presence of the fused benzo-ring of the indenyl ligand.
One might expect methyl substitution on h5-indenyl
ligands would be a significant influence on the Ti center
electrophilicity.
However, interpreting the polymerization results in
terms of electrophilicity alone leads to a dichotomy
between competing phenomena. On the one hand, a
relatively low electron density on the metal center
should enhance the electrophilicity of the catalyst,
strengthening the metal/monomer p-complex (which
might be expected to increase activity), as well as the
degree of association within both the catalyst ion-pair
and the catalyst-solvent complex (both of which might
be expected to decrease activity). On the other hand,
increasing electron density on the metal center (via
electron releasing h5-ligand substitution) should
decrease the electrophilicity of the metal center,
weakening the metal/monomer p-complex (which might
be expected to decrease activity), as well as the degree
of association within both the catalyst ion-pair and the
catalyst–solvent complex (both of which might be
expected to increase activity). Hence, determining the
controlling influences on these system phenomena
under various conditions presents a challenge.
It is not a straightforward matter to compare the
catalytic activities (A) of the activated Ti precursors
studied in this work due to the complexity of the system
involved.
Cossee and Arlman [18] proposed a mechanism in
which the increasing strength of the metal/monomer
p-complex enhances catalyst activity (Eq. 12). Studies
using substituted styrene monomers [19] are consistent
with this idea, and thus Zambelli et al. [1q–s] have
postulated that the electrophilicity of the metal center is
a key feature in styrene catalyst activity.
(12)
In addition, the degree of catalyst ion-pairing as
analyzed by Chien and Tsai [20] was shown to be an
important factor influencing polymerization activity for
metallocene catalysts (Eq. 13). Pellechia et al. [16h–l]
showed that replacing Cp ligand with the more electron
releasing Cp* ligand in half-zirconocene catalysts
greatly affected both the degree of ion-pairing and the
resulting PE activities. For the polystyryl-sodium
ion-pair in THF, the propagation rate constant for the
free cation was shown to be two or more orders of
magnitude greater than for the ion-pair [21].
In conjuction with our previous results [3], the above
results
show
that
catalytic
activity
for
a
methyl-substituted IndTiCl3 complexes reach
maximum with a single methyl-substitution on the
h5-indenyl ligand and, in general, decreases with
additional methyl-substitutions on the indenyl ligand.
The plot of log(styrene activity) versus T−p 1 for
CpTi(OBu)3 and other half-metallocenes from previous
studies [1p, 3], are convex shaped with a maxima at
Tp=50°C. Similar results were obtained in the present
study for styrene polymerizations using 9–12 (Fig. 1).
The effect of Tp is most pronounced for 1-(Pr)IndTiCl3
(10), and almost imperceptible with 1-(4%-butenyl)-
IndTiCl3 (11). The styrene polymerization behaviours
of ten other IndTiCl3 complexes were studied and the
results plotted in Figs. 2 and 3. There are three types:
(A) increases with T−p 1; (A) decreases with T−p 1; and
(A) is almost independent of T−p 1. These results
probably reflect different regions of the overall convex
dependency seen in Fig. 1. The biggest difference in (A)
is 30-fold due to a combination of steric and electronic
effects.
(13)
Both Zambelli et al. [1r] and the Baird group
[16m–n] have obtained data which show that the
degree of solvent/half-metallocene association also
influences catalyst activity. This can be described
according to Eq. 14.
(14)
To complicate matters even more, complexes
possessing several oxidation states have been shown to
be active for s-PS [16e–f, 22]. The rate of catalyst
reduction can also be influenced by h5-ligand
substitution [23].
Chien and Tsai [20] analyzed the convex dependency
of effect of polymerization activity for metallocene
catalysts on Tp in terms of the equilibria outlined in 12
and 13 and found an analytical solution which showed
two Tp domains. At low Tp both the ion-pair and

T.E. Ready et al. / Journal of Organometallic Chemistry 583 (1999) 11–27
15
Table 1
Styrene polymerizations using precursors activated with MAOa
b
c
e
Precursor
Tp (°C)
Total yield (g)
A
(×10−7
)
s-PS d (%)
Tm (°C)
(1) 1,2-(Me)2IndTiCl3
50
75
100
0.730
0.449
0.258
1.3
0.82
0.47
90.6
90.3
88.8
261.1, 271.1
260.2, 270.6
262.5, 271.2
261.1, 271.5
261.2, 271.6
(2) 1,3-(Me)2IndTiCl3
50
75
100
0.679
0.400
0.234
1.2
0.73
0.43
92.1
92.2
90.6
(3) 1,2,3-(Me)3IndTiCl3
(4) 1,3,4,7-(Me)4IndTiCl3
(5) 4,5,6,7-(Me)4IndTiCl3
50
75
100
0.070
0.188
0.279
0.13
0.35
0.51
93.3
95.7
91.1
50
75
100
0.046
0.115
0.118
0.084
0.21
0.35
92.3
93.7
90.0
50
75
100
0.240
0.465
0.494
0.44
0.85
0.90
95.4
94.1
87.0
(6) 1,2,4,5,6,7-(Me)6IndTiCl3
(7) 1,2,3,4,5,6,7-(Me)7IndTiCl3
50
75
100
50
75
100
0.0219
0.036
0.050
0.105
0.132
0.195
0.040
0.066
0.092
0.19
0.24
0.35
89.9
87.4
86.4
94.7
92.5
91.5
261.0, 270.2
262.5, 271.7
(8) Cp*TiCl3
50
75
100
0.029
0.054
0.068
0.052
0.13
0.13
95.1
92.3
89.4
262.2, 271.5
260.8, 270.6
260.3, 268.1
260.2, 271.2
(9) 1-(Allyl)IndTiCl3
0
25
50
75
100
0.036
0.119
0.255
0.231
0.227
0.067
0.22
0.47
0.42
0.42
76.0
75.2
77.5
71.4
73.5
(10) 1-(Pr)IndTiCl3
0
25
50
75
100
0.019
0.389
1.051
0.482
0.425
0.036
0.72
1.9
0.84
0.78
80.3
81.7
82.1
77.8
72.8
(11) 1-(Butenyl)IndTiCl3
(12) 1-(n-Bu)IndTiCl3
0
25
50
75
100
0.297
0.227
0.359
0.262
0.188
0.55
0.42
0.66
0.48
0.35
66.6
64.0
75.3
67.9
63.3
0
25
50
75
100
0.022
0.051
0.130
0.085
0.084
0.040
0.094
0.24
0.16
0.15
65.3
67.8
79.6
75.6
66.6
261.2, 271.2
262.2, 270.2
260.2, 268.2
(14) IndTiCl2CH3
(15) IndTiCHT
50
75
100
2.055
1.046
0.827
3.8
1.9
1.5
97.7
97.7
87.7
50
75
100
0.070
0.035
0.003
0.13
0.064
0.0055
42.5
36.0
–
a Polymerization conditions: [Ti], 50 mM; [Al]/[Ti], 4000; reaction time, 0.5 h; [styrene], 0.87 M.
b Cp*, h5-pentamethylcyclopentadienyl; Ind, h5-indenyl; Me, methyl; Pr, propyl; Bu, butyl; CHT, h7-cycloheptatrienyl.
c A (activity)=(g bulk polymer)/(mol Ti)(mol monomer)(h).
d % s-PS=[(g of 2-butanone insoluble polymer)/(g of bulk polymer)]×100.
e Tm, melting temperature of s-PS.

16
T.E. Ready et al. / Journal of Organometallic Chemistry 583 (1999) 11–27
Fig. 1. Plot of log(styrene polymerization activity) versus 1/Tp×
1000. w, (9) 1-(allyl)-IndTiCl3; (10) 1-(Pr)IndTiCl3; X, (11) 1-(4%-
But-1%-enyl)IndTiCl3; c, (12) 1-(n-bu)-IndTiCl3.
Fig. 3. Plot of log(styrene polymerization activity) versus 1/Tp×
1000. ꢁ, (6) 1,2,4,5,6,7-(Me)6-IndTiCl3; ꢂ, (7) 1,2,3,4,5,6,7-(Me)7-
IndTiCl3; 2, (8) Cp*TiCl3; X , (14) IndTiCl2CH3; Õ, (15) Ind-
Ti(C7C7).
due the difficulty in dislodging a multi-hapto ligand
during alkylation [1q, 25a,c,h].
p-complex are stable and (A) is small. Increasing Tp
promotes ion-pair dissociation ( 13) and k3 ( 12) with
consequent increase of (A). At high Tp, the p-complex
dissociates, (A) declines, and deactivation occurs via the
reduction of Ti+(IV) species to Ti(III) products [25].
IndTi(CH3)Cl2 (14), used in conjunction with trityl-
tetrakis-(pentafluorophenyl)borate co-catalyst was inac-
tive toward styrene, presumably due to the inability of
the coordinated monomer to migratory insert with an-
other alkyl ligand. The instability of IndTi(CH3)3 (13)
precluded reproducible polymerization data as well and
so they are not reported.
The styrene stereoselectivities of the indenyl catalysts
were high, although those for catalysts with bulky
substituents (9–12) were more moderate. The styrene
stereoselectivity for IndTiCHT was very low. Styrene
stereoselectivity of all of the catalysts decreased at
100°C as compared to 50°C and half of the catalysts
show some loss of stereospecificity at 75°C.
MAO activated ethylene polymerization results for
catalysts with h5-ligands containing pendant olefin sub-
stituents (9, 11) and their saturated analogs (10, 12) are
reported in Table 2.
h5-Indenyl-h7-cycloheptatrienyltitanium (15) demon-
strated a very low activity toward styrene. This is
probably the result of slow activation of the precursor
Catalyst precursors (9, 11) equipped with h5-ligands
containing pendant olefin substituents, ostensibly,
might be expected to exhibit polymerization character-
istics similar to other catalysts with coordinating pen-
dant substituents such as (Me2NCH2CH2–)CpTiCl3
[26a,b] and particularly, (C6H5CH2CH2)CpTiCl3 [26c].
If so, s-PS activity should be suppressed and ethylene
activity enhanced compared to the corresponding com-
plexes (10,12) possessing indenyl ligands with
analogous saturated pendant substituents. The steric
bulk of the ligands in 9–12 would be expected to limit
monomer coordination and/or migratory insertion pro-
cesses producing very low s-PS activities [3a].
However, catalyst precursors 9 and 11 exhibited a
very low magnitude of activity for both s-PS and PE.
The low PE and PP activity for 9 and 11 is consistent
with the low activities seen for these monomers using
half-metallocenes in general, and is considerably lower
than that reported for (C6H5CH2CH2)CpTiCl3 [26c].
Although there are some slight differences seen in
activities between 9 and 11 versus 10 and 12, respec-
tively, these differences fall close to the magnitude
which may be expected for uncertainty in this system,
and they do not always follow the expected trend.
Fig. 2. Plot of log(styrene polymerization activity) versus 1/Tp×
1000. ꢃ, (1) 1,2-(Me)2IndTiCl3; “, (2) 1,3-(Me)2IndTiCl3; ꢄ, (3)
1,2,3-(Me)2IndTiCl3; ", (4) 1,3,4,7-(Me)4IndTiCl3; ꢅ, (5) 4,5,6,7-
(Me)4IndTiCl3.

T.E. Ready et al. / Journal of Organometallic Chemistry 583 (1999) 11–27
17
These results lead one to conclude that any coordina-
3.2. Synthesis of 1,2-dimethylindene (I) [11o]
tion by the pendant olefin substituents in 9 and 11 is
limited at best and not sufficient to promote oligomer-
izations of a-olefin monomers. The limited coordina-
tion (if at all) of these restricted olefins cannot compete
effectively with the more powerful coordination of un-
restricted arene solvents [1o,p,r] or monomers [16m–o].
Benzene (300 ml, 3.35 mol) and aluminum trichloride
(80 g, 0.6 mol) were introduced into a three neck 500 ml
round bottom flask fitted with a magnetic stirring ap-
paratus, an addition funnel, and a reflux condenser.
The stirred mixture was cooled to 0°C and 27 g of
tigloyl chloride (0.31 mol) was added dropwise via the
addition funnel. After the addition was complete, the
mixture was allowed to warm to room temperature and
then refluxed overnight. The mixture was cooled to
room temperature and poured into a 1000 ml beaker
containing 300 g of ice and 50 ml of concentrated
hydrochloric acid. The organic layer was extracted
three times with 100 ml portions of a saturated solution
of sodium bicarbonate, then dried over anhydrous mag-
nesium sulfate. The excess benzene was removed under
reduced pressure to leave an orange oil of 2,3-dimethyl-
1-indanone (41 g, 0.26 mol, 84% yield).
3. Experimental
All operations were carried out under argon atmo-
sphere using standard Schlenk and glove box tech-
niques unless otherwise noted. Methylene chloride was
distilled under argon from calcium hydride. All other
solvents were distilled under argon form sodium–potas-
sium alloy. TiCl4 was distilled (trap to trap) from
copper turnings prior to use. Elemental analyses were
performed by the Microanalytical Laboratory, Univer-
1
sity of Massachusetts, Amherst, MA. H-NMR spectra
A diethyl ether solution (100 ml) of 2,3-dimethyl-1-
indanone (20 g, 0.125 mol) was added dropwise via
syringe under argon to a 500 ml side-armed round-bot-
tomed flask containing a stirred slurry of lithium alu-
minum hydride (5.7 g, 0.15 mol) in 250 ml of diethyl
ether, fitted with a magnetic stirring apparatus and a
reflux condenser with a gas outlet valve connected to a
mercury overpressure bubbler. The mixture was
refluxed overnight, cooled to 0°C, and 100 ml of water
was added dropwise through the top of the condenser
(caution!). The organic layer was washed three times
with 100 ml portions of water and dried over anhy-
drous magnesium sulfate. The ether was removed under
reduced pressure to leave a yellow residue of 2,3-
dimethyl-1-indanol (16.5 g, 0.102 mol, 82% yield).
Toluene (300 ml) was added to the indanol residue
and the solution was poured into a 500 ml round-bot-
tom flask fitted with a magnetic stirring apparatus and
a Dean–Stark apparatus. A catalytic amount of p-
toluenesulfonic acid (50 mg) was added and the solu-
tion refluxed for 5 h at which time the water layer was
removed and excess toluene distilled via the Dean–
Starke arm. After the mixture was cooled, the organic
were obtained on a Bruker NR-80 spectrometer. Melt-
ing points of the polymers were obtained using a Perkin
Elmer model DSC-4 differential scanning calorimeter.
3.1. Synthesis of tigloyl chloride, crotonoyl chloride,
and acryloyl chloride
In a fume hood, thionyl chloride (300 ml, 4.11 mol)
and 100 g of the appropriate acid (0.998 mol tiglic acid;
1.16 mol crotonic acid; 1.16 mol, 98.5 ml, methacrylic
acid; 1.39 mol, 95 ml acrylic acid) were introduced into
a 500 ml round bottom flask fitted with a magnetic
stirring apparatus and a reflux condenser. The mixture
was refluxed for 15 h at which time the reflux condenser
was replaced with a distillation head and condenser.
Excess thionyl chloride was distilled at 78°C and ambi-
ent pressure, followed by the resulting acid chloride
(methacryloyl chloride: 95–96°C; crotonoyl chloride:
118–125°C; tigloyl chloride: 130–140°C). In the case of
acryloyl chloride, the excess thionyl chloride was re-
moved under vacuum (25°C, 0.01 mmHg), followed by
acryloyl chloride (35–40°C, 0.01 mmHg).
Table 2
Ethylene polymerizations using precursors activated with MAOa,b
Temperature (°C)
Activity (×10−4) (g PE/{(mol Ti)([ethylene])(h)})
1-(Allyl)IndTiCl3 (9)
1-(Pr)IndTiCl3 (10)
1-(Butenyl)IndTiCl3 (11)
1-(Bu)IndTiCl3 (12)
0
25
50
5.5
3.5
2.5
5.0
3.0
3.9
1.3
1.2
1.7
0.62
0.35
0.14
a Polymerization conditions: [Ti], 50 mM; Al/Ti, 4000, ethylene, 15 psig; total reaction volume, 50 ml; reaction time, 2 h.
b Ind, h5-indenyl; Me, methyl; Pr, propyl; Bu, butyl; Butenyl, 1-4%-butenyl.

18
T.E. Ready et al. / Journal of Organometallic Chemistry 583 (1999) 11–27
residue was washed three times with 100 ml portions of
saturated sodium bicarbonate solution and dried over
anhydrous magnesium sulfate. The dark yellow residue
was distilled under vacuum (90–95°C, 0.01 mmHg) to
give a pale yellow fraction of 1,2-dimethylindene (I,
removed and excess toluene distilled via the Dean–
Stark arm. After the mixture was cooled, the organic
residue was dissolved into 100 ml of diethyl ether,
washed three times with 100 ml portions of saturated
sodium bicarbonate solution and dried over anhydrous
magnesium sulfate. The ether was removed under re-
duced pressure, and the dark yellow residue was dis-
tilled under vacuum (90–95°C, 0.01 mmHg) to give a
pale yellow fraction of 1,3-dimethylindene (II, 15.0 g,
0.104 mol, 75% yield, 51.5% overall yield).1H-NMR
(CDCl3): l 7.36–7.20 (m, 4H, arom.), 6.11 (s, 1H, sp2
2-position), 3.40 (q, 1H, sp3 1-position, J(1-1-position
CH3)=7.5 Hz), 2.12 (s, 3H, 3-position CH3), 1.27 (d,
3H, 1-position CH3, J(1-position CH3-1)=7.5 Hz).
1
12.1 g, 0.085 mol, 83% yield, 57% overall yield). H-
NMR: (CDCl3) l 7.4–7.05 (m, 4H, arom.), 6.41 (m,
1H, sp2 3-position, J(3-2-position CH3=0.68 Hz, J(3–
1)=0.68 Hz), 3.21 (qm, 1H, sp3 1-position, J(1-1-posi-
tion CH3=8.0 Hz, J(1–3)=0.68 Hz, J(1-2-position
CH3)=0.68 Hz), 2.055 (dd, 3H, 2-position CH3,
J(CH3-1)=0.68 Hz, J(CH3-3)=0.68 Hz), 1.28 (d, 3H,
1-position CH3, J(CH3-1)=8.0 Hz).
3.3. Synthesis of 1,3-dimethylindene (II)
3.3.2. Method B [5d, 11a]
3.3.1. Method A [11j, 27]
Butyllithium (48 ml, 1.6 M in hexane, 0.077 mol) was
added dropwise via a syringe to a hexane solution (150
ml) of 3-methylindene [3a] (10 g, 0.077 mol) contained
in a 500 ml side-armed flask fitted with a gas outlet
connected to a mercury overpressure valve. The solu-
tion was allowed to stir overnight at room temperature
which produced a white precipitate of 1-methylindenyl-
lithium. The supernatent liquid was removed using a
filter cannula and replaced with 200 ml of THF. (Note:
The solvation of a dry lithium salt in THF is exothermic
and may require cooling.) Iodomethane (5.0 ml, 0.08
mol) was added dropwise via syringe to the THF
solution containing the lithium salt and the reaction
mixture allowed to stir overnight at room temperature.
The THF was removed under reduced pressure and
replaced with 200 ml of hexane. Butyllithium (48 ml, 1.6
M in hexane, 0.077 mol) was added dropwise via a
syringe and the mixture allowed to stir overnight result-
ing in a white precipitate of 1,3-dimethylindenyllithium.
The supernatant liquid was removed using a filter can-
nula and discarded. The white precipitate was washed
twice with 100 ml portions of hexane which were
removed using a filter cannula and discarded. Hexane
(200 ml) was introduced to the lithium salt followed by
the addition of 100 ml of water in small portions
through the top of the flask. The hexane–water solution
was vigorously stirred for 30 min after which the hexane
fraction was isolated using a separatory funnel and
dried over anhydrous MgSO4. The hexane was removed
under reduced pressure and the residue distilled under
vacuum (90–95°C, 0.01 mmHg) to give a pale yellow
fraction of 1,3-dimethylindene (II, 7.2 g, 0.055 mol, 72%
yield). The 1H-NMR spectrum of the product was
identical to that for II obtained by Method A.
Benzene (300 ml, 3.35 mol) and aluminum trichloride
(80 g, 0.60 mol) were introduced into to a three neck
500 ml round bottom flask fitted with a magnetic
stirring apparatus, an addition funnel, and a reflux
condenser. The stirred mixture was cooled to 0°C and
27 g of crotonyl chloride (19.4 ml, 21.14 g, 0.20 mol)
was added dropwise via the addition funnel. After the
addition was complete, the mixture was allowed to
come to room temperature and then refluxed overnight.
The mixture was cooled to room temperature and
poured into a 1000 ml beaker containing 300 g of ice
and 50 ml of concentrated hydrochloric acid. The or-
ganic layer was extracted three times with 100 ml
portions of a saturated solution of sodium bicarbonate
then dried over anhydrous magnesium sulfate. The
excess benzene was removed under reduced pressure to
leave an orange oil of 3-methyl-1-indanone (25.8 g,
0.178 mol, 88% yield).
Diethyl ether (250 ml), and 20 g, 0.138 mol of
3-methyl-1-indanone were added under argon to a 500
ml side-armed round-bottomed flask fitted with a mag-
netic stirring apparatus and a reflux condenser with a
gas outlet valve connected to a mercury overpressure
bubbler. Methyl lithium (143 ml, 1.4 M in diethyl ether,
0.20 mol) was added dropwise via syringe and the
mixture was refluxed overnight. The mixture was cooled
to 0°C and 100 ml of saturated amonium chloride
solution was added dropwise through the top of the
condenser. The organic layer was washed three times
with 100 ml portions of water and dried over anhydrous
magnesium sulfate. The ether was removed under re-
duced pressure to leave a yellow residue of 1,3-
dimethyl-1-indanol (20.3 g, 0.139 mol, 78% yield).
Toluene (300 ml) was added to the indanol residue
and the solution was poured into a 500 ml round-bot-
tom flask fitted with a magnetic stirring apparatus and
a Dean–Stark apparatus. A catalytic amount of p-
toluenesulfonic acid (50 mg) was added and the solution
refluxed for 5 h at which time the water layer was
3.4. Synthesis of 1,2,3-trimethylindene (III) [4d]
Utilizing the procedure for 1,3-dimethylindene
(Method A), 2,3-dimethyl-1-indanone was prepared in
84% yield (41 g) from benzene (300 ml, 3.35 mol),

T.E. Ready et al. / Journal of Organometallic Chemistry 583 (1999) 11–27
19
aluminum trichloride (80 g, 0.6 mol) and tigloyl chlo-
ride (27 g, 0.31 mol). A subsequent reaction of 2,3-
dimethyl-1-indanone (15.0g, 0.0938 mol) in 250 ml of
diethyl ether with methyl lithium (71 ml, 1.4 M in
diethyl ether, 0.10 mol) followed by hydrolysis afforded
1,2,3-trimethyl-1-indanol in 86% yield (14.2 g) as a
yellow residue. Dehydration of the indanol residue in
300 ml of toluene containing 50 mg of p-toluenesulfonic
acid followed by distillation (92–98°C, 0.01 mmHg)
gave a pale yellow fraction of 1,2,3-trimethylindene
(III, 10.05 g, 0.0635 mol, 79% yield, 57.1% overall yield
(15.6 g, 82% yield). Dehydration and work-up of the
indanol produced a dark yellow residue, which was
distilled under vacuum (90–95°C, 0.01 mmHg) to give
a pale yellow fraction of 11.36 g of 4,5,6,7-te-
1
tramethylindene (V, 81% yield, 60% overall yield). H-
NMR: (CDCl3)
l
7.00 (dt, 1H, sp2 3-position,
J(3-2)=5.62 Hz, J(3-1)=2.00 Hz), 6.47 (dt, 1H, sp2
2-position, J(2-3)=5.62 Hz, J(2-1)=1.90 Hz), 3.33
(unresolved dd, 2H, sp3 1-position, J(1-3)=2.00 Hz,
J(1-2)=1.90 Hz), 2.38 (s, 3H, 4-positon CH3), 2.30 (s,
3H, 7-position CH3), 2.26 (s, 3H, 6-position CH3), 2.20
(m, 3H, 5-position CH3).
1
based on tigloyl chloride). H-NMR: (CDCl3) l 7.53–
7.0 (m, 4H, arom.), 3.17 (q, 1H, sp3 1-position, J(1-1-
position CH3)=7.44 Hz), 2.02 (q, 3H, 2-position CH3,
J(2-position CH3-3-position CH3)=0.96 Hz), 1.97 (q,
3H, 3-position CH3, J(3-position CH3-2-position
CH3=0.96 Hz), 1.30 (d, 3H, 1-position CH3, J(1-posi-
tion CH3-1)=7.44 Hz).
3.7. Synthesis of 2,3,4,5,6,7-hexamethylindene (VI)
The method of preparation is the same as for 1,2-
dimethylindene except that 1,2,3,4-tetramethylbenzene
(300 ml, 1.99 mol) and aluminum trichloride (56 g, 0.42
mol) were used in conjuction with 25 g of tigloyl
chloride (0.21 mol) to produce an orange oil of
2,3,4,5,6,7-hexamethyl-1-indanone (58.3 g, 87% yield).
The indanone (15 g, 0.065 mol) was in turn reacted
with lithium aluminum hydride (3.00 g, 0.0791 mol),
which upon work-up produced a yellow residue of
2,3,4,5,6,7-hexamethyl-1-indanol (12.6 g, 89% yield).
Dehydration and subsequent work-up of the indanol
produced 9.02 g of crude 1,2,4,5,6,7-hexamethylindene
(this isomer is assumed based on the starting materials)
as a yellow oil 78, 60% overall yield). Purification of the
crude 1,2,4,5,6,7-hexamethylindene by vacuum distilla-
tion (220–225°C, 0.01 mmHg) resulted in isomerization
to 2,3,4,5,6,7-hexamethylindene (VI), collected as a pale
yellow oil which solidified on cooling. 1H-NMR:
(CDCl3) l 3.11 (s, 2H, sp3 1-position), 2.49 (s, 3H,
4-position CH3), 2.30 (s, 3H, 7-position CH3), 2.23 (s,
6H, overlapping 5 and 6-position CH3), 2.21 (s, 3H,
2-position CH3), 2.02 (s, 3H, 3-position CH3).
3.5. Synthesis of 1,3,4,7-tetramethylindene (IV)
The method of preparation was the same as for
1,3-dimethylindene (Method A) except that p-xylene
(200 ml, 1.63 mol) and aluminum trichloride (26.7 g,
0.2 mol) were used in conjunction with 10 g of crotonyl
chloride (0.096 mol) to produce 14.5 g (87.5% yield) of
3,4,7-trimethyl-1-indanone as an orange oil. The in-
danone was in turn reacted with methyl lithium (64.3
ml, 1.4 M in diethyl ether, 0.09 mol) and the subse-
quent work-up produced a yellow residue of 1,3,4,7-te-
tramethyl-1-indanol (13 g, 82% yield). Dehydration and
work-up of the indanol produced a dark yellow residue,
which was distilled under vacuum (92–98°C, 0.01
mmHg) to give a pale yellow fraction of 1,3,4,7-te-
tramethylindene (IV, 9.2 g, 78% yield, 56% overall
1
yield). H-NMR: (CDCl3) l 6.68 (m, 2H, arom.), 6.05
(m, 1H, sp2 2-position, J(2-1)=1.92 Hz, J(2-3-position
CH3)=1.68 Hz), 3.38 (qm, 1H, sp3 1-position, J(1-1-
position CH3)=7.28 Hz, J(1-2)=1.92 Hz, J(1-3-posi-
ton CH3)=1.68 Hz), 2.53 (s, 3H, 4-position CH3), 2.36
(s, 3H, 7-position CH3), 2.29 (dd, 3H, 3-position CH3,
J(3-position CH3-1)=1.68 Hz, J(3-position CH3-2)=
1.68 Hz), 1.24 (d, 3H, 1-position CH3, J(1-position
CH3-1)=7.28 Hz).
3.8. Synthesis of 1,2,3,4,5,6,7-heptamethylindene (VII)
[4c–f ]
The method of preparation was the same as for
1,3-dimethylindene (Method A) except that 1,2,3,4-te-
tramethylbenzene (300 ml, 1.99 mol) and aluminum
trichloride (56 g, 0.42 mol) were used in conjunction
with 25 g of tigloyl chloride (0.21 mol) to produce an
orange oil of 2,3,4,5,6,7-hexamethyl-1-indanone (58.3 g,
87% yield). The indanone (15 g, 0.065 mol) was in turn
reacted with methyl lithium (50.0 ml, 1.4 M in diethyl
ether, 0.07 mol), which after work-up produced a yel-
low residue of 1,2,3,4,5,6,7-heptamethyl-1-indanol
(11.67 g, 84% yield). Dehydration and subsequent
work-up of the indanol produced a dark yellow residue
of crude 1,2,3,4,5,6,7-heptamethylindene as a yellow oil
(VII, 9.22 g, 79% yield, 58% overall yield). The crude
heptamethylindene was recrystallized from methanol to
3.6. Synthesis of 4,5,6,7-tetramethylindene (V)
The method of preparation was the same as for
1,2-dimethylindene except that 1,2,3,4-tetramethylben-
zene (200 ml, 1.33 mol) and aluminum trichloride (29 g,
0.22 mol) were used in conjuction with 10 g of acryloyl
chloride (0.111 mol) to produce an orange oil of
4,5,6,7-tetramethyl-1-indanone (18.8 g, 90% yield). The
indanone was in turn reacted with lithium aluminum
hydride (4.5 g, 0.12 mol), which upon work-up pro-
duced a yellow residue of 4,5,6,7-tetramethyl-1-indanol

20
T.E. Ready et al. / Journal of Organometallic Chemistry 583 (1999) 11–27
give a pale yellow powder. 1H-NMR: (CDCl3) l 3.15 (q,
1H, sp3 1-position, J(1-1-position CH3)=2.8 Hz), 2.48
(s, 3H, 4-position CH3), 2.30 (s, 3H, 7-position CH3),
2.22 (bs, 9H, overlapping 2, 5, and 6-position CH3), 1.93
(s, 3H, 3-position CH3), 1.21 (d, 3H, 1-position CH3,
J(1-position CH3-1)=2.8 Hz).
at 0°C. After the addition was completed, the mixture
was allowed to warm to room temperature and stirred
overnight. The THF was removed under vacuum and
replaced with 100 ml of hexane. The solution was passed
through a silica gel column and a bright yellow band was
collected. The hexane was removed under vacuum to
yield 5.7 g (81%) of a yellow oil. This residue was
distilled at 75–76°C/0.001 mmHg to give a colorless oil
which turned yellow on standing at room tempera-
ture.1H-NMR (CDCl3): l 7.4–7.2 (m, 4H, arom.),
6.22 (bs, 1H, sp2 2-position), 5.95 (m, 1H,
–CH2CH2CHꢀCH2, J(2%-1%trans)=8.2 Hz), 5.12 (d of
m, 1H, –CH2CH2CHꢀCHH trans, J(1%trans-2%)=8.2
3.9. Synthesis of 1-allylindene (VIII)
A suspension of 10.0 g (0.082 mol) of indenyllithium
in 250 ml of hexane contained in a 500 ml side-armed
flask fitted with an overpressure bubbler was chilled to
0°C. 3-Chloropropene (also called allyl chloride, 6.7 ml,
0.082 mol) was added dropwise via syringe to the flask
and the mixture allowed to stir overnight at room
temperature. The solution was filtered through a Celite
plug and the hexane removed under vacuum to yield 4.26
g (68%) of a yellow oil. The product was distilled at
62–65°C/0.001 mmHg and a colorless oil was obtained
which turned yellow on standing at room temperature.
1H-NMR (CDCl3): l 7.61–7.00 (m, 4H, arom.), 6.80
(dd, 1H, sp2 3-position, J(3-2)=5.6 Hz, J(3-1)=1.5
Hz), 6.51 (dd, 1H, sp2 2-position, J(2-3)=5.6 Hz,
J(2-1)=1.7 Hz), 6.23–5.60 (complex m, 1H, sp2 –CH2–
CHꢀCH2, J(2%-1%trans)=7.0 Hz, J(2%-CH2)=6.7 Hz),
5.22 (d of m, 1H, sp2, –CH2–CHꢀCH2 trans, J(1%trans-
2%)=7.2 Hz, J(1%-1%)=1.0 Hz), 4.96 (m, 1H, sp2, –CH2–
CHꢀCH2 cis, J(1%-1%gem)=1.0 Hz), 3.46 (m, 1H, sp3
1-position, J(1-CH2)=7.2 Hz, J(1-2)=1.7 Hz, J(1-
3)=1.5 Hz), 2.47 (complex m, 2H, sp3, –CH2–
CHꢀCH2, J(CH2-1)=7.2 Hz, J(CH2-2%=6.7 Hz).
Hz,
J(1%-1%gem)=0.9
Hz),
4.95
(m,
1H,
–CH2CH2CHꢀCHH cis, J(1%-1%)=0.9 Hz), 3.32 (t of m,
2H, sp3 1-position, J(1%-4%)=1.4 Hz, 2.8–2.4 (m of m,
4H, –CH2CH2CHꢀCH2, overlapping signals, J(4%-1%)=
1.4 Hz).
3.12. Synthesis of 1-n-Butylindene (X) [5c]
The method of preparation was the same as for
1-allylindene except that 10.0 g (0.082 mol) of indenyl-
lithium was reacted with 1-bromobutane (9.0 ml, 0.082
mol) producing a yellow oil. The product was distilled
at 75–76°C/0.001 mmHg and a colorless oil was ob-
tained which turned yellow on standing at room temper-
1
ature. H-NMR (CDCl3): l 7.38 (m, 2H, arom.), 7.23
(m, 2H, arom.), 6.78 (d, 1H, sp2 3-position, J(3-2)=5.52
Hz), 6.52 (d, 1H, sp2 2-position, J(2-3)=5.52 Hz), 3.45
(m, 1H, sp3 1-position, J(1-1%)=4.2 Hz), 1.86 (m, 2H,
–CH2CH2CH2CH3, J(1%-1)=4.2 Hz), 1.62–1.20 (m, 4H,
overlapping signals –CH2CH2CH2CH3, J(3%-4%)=3.2
Hz), 0.96 (t, 3H, –CH2CH2CH2CH3, J(4%-3%)=3.2 Hz).
3.10. Synthesis of 1-n-propylindene (IX) [5c,d]
The method of preparation was the same as for
1-allylindene except that 10.0 g (0.082 mol) of indenyl-
lithium was reacted with 1-chloropropane (7.4 ml, 0.082
mol) to yield 9.1 g (72%) of a yellow oil. The product was
distilled at 71–72°C/0.001 mmHg and a colorless oil was
obtained which turned yellow on standing at room
3.13. Synthesis of 1-trimethylsilyl-2,3-dimethylindene
(XII)
Butyllithium (44 ml, 1.6 M in hexane, 0.07 mol) was
added to a solution of 1,2-dimethylindene (I, 10 g, 0.069
mol) in 100 ml of THF contained in a magnetically
stirred 200 ml side-armed round-bottomed flask fitted
with a gas-outlet valve connected to a mercury overpres-
sure valve. After the solution had stirred for 4 h,
chlorotrimethylsilane (10.2 ml, 0.08 mol) was added to
the flask via a syringe and stirring was continued
overnight. The THF and excess chlorotrimethylsilane
were removed under reduced pressure, replaced with 100
ml of dry hexane, and stirred for 15 min. The hexane
solution was filtered using a filter cannula and the
solvent was removed under reduced pressure to yield
1-trimethylsilyl,2,3-dimethylindene as a yellow oil (11.6
g, 0.053 mol, 77% yield). 1H-NMR: (CDCl3) l 7.45–7.15
(m, 4H, arom.), 3.34 (bs, 1H, sp3 1-position), 2.19 (bs,
6H, overlapping 2 and 3-position CH3), 0.05 (s, 9H,
Si(CH3)3).
1
temperature. H-NMR (CDCl3): l 7.38 (m, 2H, arom.),
7.23 (m, 2H, arom.), 6.78 (d, 1H, sp2 3-position, J(3-
2)=5.52 Hz), 6.52 (d, 1H, sp2 2-position, J(2-3)=5.52
Hz), 3.45 (m, 1H, sp3 1-position, J(1-1%)=4.2 Hz,
J(1-2)=1.8 Hz, J(1-3)=1.8 Hz), 1.86 (m, 2H,
–CH2CH2CH3, J(1%-1)=4.2 Hz, J(1%-2%)=2.2 Hz), 1.46
(m, 2H, –CH2CH2CH3, J(2%-1%)=2.2 Hz, J(2%-3%)=3.2
Hz), 0.96 (t, 3H, –CH2CH2CH3, J(3%-2%)=3.2 Hz).
3.11. Synthesis of 3-(4%-n-but-1%-enyl)indene (XI)
THF (250 ml) was added to 5.0 g (0.041 mol) of
indenyllithium in a 500 ml side-armed flask fitted with
an overpressure bubbler and previously chilled to 0°C.
4-Bromo-1-butene (4.2 ml, 0.041 mol) was added to the
flask dropwise via a syringe maintaining the temperature

T.E. Ready et al. / Journal of Organometallic Chemistry 583 (1999) 11–27
21
3.14. Synthesis of 1-trimethylsilyl-1,3-dimethylindene
(XIII)
3H, 7-position CH3), 2.34 (d, 3H, 3-position CH3,
J(3-position CH3-2)=1.20 Hz), 1.55 (s, 3H, 1-position
CH3), −0.13 (s, 9H, Si(CH3)3).
1,3-Dimethylindene (II, 5.0 g, 0.035 mol) was dis-
solved in 100 ml of hexane contained in a 250 ml
side-armed flask fitted with a gas inlet connected to an
overpressure bubbler. To this solution 27.1 ml of 1.6 M
n-butyllithium (0.035 mol) was added dropwise and the
mixture was stirred overnight at room temperature. The
supernatant liquid was decanted and the white precipi-
tate was washed with three 100 ml portions of hexane.
Fresh hexane (100 ml) was introduced to the flask, 5.5
ml (0.043 mol) of chlorotrimethylsilane was added
dropwise via a syringe to the stirred suspension, and the
mixture was allowed to stir overnight. The solution was
then filtered through a Celite plug and the solvent
removed under vacuum, leaving 6.23 g (0.0287 mol,
82% yield) of a yellow oil. The crude product was
further purified via distillation at 87–88°C/0.001
mmHg to yield a colorless oil which darkened on
standing at room temperature. 1H-NMR: (CDCl3) l
7.26 (m, 4H, arom.), 6.16 (d, 1H, sp2 2-position, J(2-3-
position CH3)=1.4 Hz), 2.18 (d, 3H, 3-position CH3,
J(CH3-2)=1.4 Hz), 1.42 (s, 3H, 1-position CH3), −
0.16 (s, 9H, Si(CH3)3).
3.17. Synthesis of 1-trimethylsilyl-4,5,6,7-
tetramethylindene (XVI)
The method of preparation was the same as for
1-trimethylsilyl-2,3-dimethylindene except that butyl-
lithium (18.8 ml, 1.6 M in hexane, 0.03 mol) was
reacted with 4,5,6,7-tetramethylindene (V, 5.0 g, 0.029
mol), followed by reaction with chlorotrimethylsilane
(5.1 ml, 0.04 mol). Work-up of the residue yielded
1-trimethylsilyl-4,5,6,7-tetramethylindene as a yellow oil
1
(4.1 g, 82% yield). H-NMR: (CDCl3) l 7.02 (dd, 1H,
sp2 3-position, J(3-2)=6.00 Hz, J(3-1)=1.48 Hz), 6.60
(dd, 1H, sp2 2-position, J(2-3)=6.00 Hz, J(2-1)=1.98
Hz), 3.71 (m, 1H, sp3 1-position, J(1-2)=1.98 Hz,
J(1-3)=1.48 Hz). 2.47 (s, 3H, 4-position CH3), 2.37 (s,
3H, 7-position CH3), 2.32 (s, 6H, overlapping 5- and
6-position CH3), −0.04 (s, 9H, Si(CH3)3).
3.18. Synthesis of 1-trimethylsilyl-2,3,4,5,6,7-
hexamethylindene (XVII)
3.15. Synthesis of 1-trimethylsilyl-1,2,3-trimethylindene
(XIV)
The method of preparation was the same as for
1-trimethylsilyl-2,3-dimethylindene except that butyl-
lithium (13.8 ml, 1.6 M in hexane, 0.022 mol) was
reacted with 2,3,4,5,6,7-hexamethylindene (VI, 4.0 g,
0.020 mol), followed by reaction with chlorotrimethylsi-
lane (3.2 ml, 0.025 mol). Work-up of the residue yielded
1-trimethylsilyl-2,3,4,5,6,7-hexamethylindene as a yel-
The method of preparation was the same as for
1-trimethylsilyl-2,3-dimethylindene except that butyl-
lithium (21.9 ml, 1.6 M in hexane, 0.035 mol) was
reacted with 1,2,3-trimethylindene (III, 5.0 g, 0.032
mol), followed by reaction with chlorotrimethylsilane
(5.1 ml, 0.04 mol). Work-up of the residue yielded
1-trimethylsilyl-1,2,3-trimethylindene as a yellow oil
1
low oil (4.01 g, 73% yield). H-NMR: (CDCl3) l 3.35
(s, 1H, 1-position), 2.52 (s, 3H, 4-position CH3), 2.24 (s,
3H, 7-position CH3), 2.21 (s, 6H, overlapping 5 and
6-position CH3), 2.18 (s, 3H, 2-postion CH3), 2.04 (s,
3H, 3-position CH3), −0.10 (s, 9H, Si(CH3)3).
1
(5.15 g, 70% yield). H-NMR: (CDCl3) l 7.44–7.22 (m,
4H, arom.), 2.19 (m, 3H, 2-position CH3, J(2-position
CH3-3-position CH3)=0.91 Hz), 2.11 (m, 3H, 3-pos-
tion CH3, J(3-position CH3-2-position CH3)=0.91
Hz), 1.55 (s, 3H, 1-position CH3), −0.04 (s, 9H,
Si(CH3)3).
3.19. Synthesis of 1-trimethylsilyl-1,2,3,4,5,6,7-
heptamethylindene (XVIII) [4f ]
3.16. Synthesis of 1-trimethylsilyl-1,3,4,7-
tetramethylindene (XV)
The method of preparation was the same as for
1-trimethylsilyl-2,3-dimethylindene except that butyl-
lithium (15 ml, 1.6 M in hexane, 0.024 mol) was reacted
with 1,2,3,4,5,6,7-heptamethylindene (VII, 5.0 g, 0.023
mol), followed by reaction with chlorotrimethylsilane
(3.6 ml, 0.028 mol). Work-up of the residue yielded
The method of preparation was the same as for
1-trimethylsilyl-2,3-dimethylindene except that butyl-
lithium (18.8 ml, 1.6 M in hexane, 0.03 mol) was
reacted with 1,3,4,7-tetramethylindene (IV, 5.0 g, 0.029
mol), followed by reaction with chlorotrimethylsilane
(5.1 ml, 0.04 mol). Work-up of the residue yielded
1-trimethylsilyl-1,3,4,7-tetramethylindene as a yellow oil
1-trimethylsilyl-1,2,3,4,5,6,7-heptamethylindene as
a
yellow oil (4.79 g, 71% yield). 1H-NMR: (CDCl3) l 2.52
(s, 3H, 4-position CH3), 2.33 (s, 3H, 7-position CH3),
2.25 (s, 3H, 5-position CH3), 2.24 (s, 3H, 6-position
CH3), 2.21 (s, 3H, 2-position CH3), 1.91 (s, 3H, 3-posi-
tion CH3), 1.565 (s, 3H, 1-position CH3), −0.17 (s, 9H,
Si(CH3)3).
1
(3.58 g, 71.7% yield). H-NMR: (CDCl3) l 6.63 (s, 2H,
arom.), 6.03 (d, 1H, sp2 2-position, J(2-3-position
CH3)=1.20 Hz), 2.56 (s, 3H, 4-position CH3), 2.40 (s,

22
T.E. Ready et al. / Journal of Organometallic Chemistry 583 (1999) 11–27
3.20. Synthesis of 1-trimethylsilyl-3-allylindene (XIX)
–CH2CH2CHꢀCH2, overlapping signals, J(4%-1%)=1.4
Hz), 0.01 (s, 9H, Si(CH3)3).
Butyllithium (8.0 ml, 1.6 M in hexane, 0.013 mol)
was added to a 100 ml solution of 1-allylindene (VIII,
2.0 g, 0.013 mol) in THF contained in a magnetically
stirred 200 ml side-armed round bottom flask fitted
with a gas-outlet valve connected to a mercury over-
pressure valve. After the solution had stirred for 4 h,
chlorotrimethylsilane (2.0 ml, 0.016 mol) was added to
the flask via a syringe and stirring was continued
overnight. The THF and excess chlorotrimethylsilane
were removed under reduced pressure, replaced with
100 ml of dry hexane, and stirred for 15 min. The
hexane solution was filtered using a filter cannula and
the solvent was removed under reduced pressure to
3.23. Synthesis of 1-trimethylsilyl-3-n-butylindene
(XXII)
The method of preparation was the same as for
1-trimethylsilyl-2,3-dimethylindene except butyllithium
(7.5 ml, 1.6 M in hexane, 0.012 mol) was reacted with
1-n-butylindene (X, 2.0 g, 0.012 mol) to produce the
lithium indene, followed by reaction with chloro-
trimethylsilane (1.5 ml, 0.012 mol). Work-up of the
residue yielded 1-trimethylsilyl-3-n-butyllindene as a
1
yellow oil. H-NMR (CDCl3): l 7.38 (m, 2H, arom.),
7.23 (m, 2H, arom.), 6.37 (s, 1H, sp2 2-position),
3.45 (m, 1H, sp3 1-position), 2.13 (t, 2H,
–CH2CH2CH2CH3, J(1%-2%)=4.2 Hz), 1.75–1.50 (m,
4H, overlapping signals –CH2CH2CH2CH3, J(3%-4%)=
3.2 Hz), 1.09 (t, 3H, –CH2CH2CH2CH3, J(4%-3%)=3.2
Hz), 0.01 (s, 9H, Si(CH3)3).
1
yield 1-trimethylsilyl-3-allylindene as a yellow oil. H-
NMR (CDCl3): l 7.55-7.15 (m, 4H, arom.), 6.38 (s, 1H,
sp2 2-position), 6.30–5.81 (complex m, 1H, sp2, –CH2–
CHꢀCH2), 5.27 (m, 1H, sp2, –CH2–CHꢀCH2 trans),
5.17 (m, 1H, sp2, –CH2–CHꢀCH2 cis), 3.45 (s, 1H, sp3
1-position), 3.35 (m, 2H, sp3, –CH2–CHꢀCH2), 0.01 (s,
9H, Si(CH3)3).
3.24. Synthesis of 1,2-dimethylindenyltrichlorotitanium
(1)
3.21. Synthesis of 1-trimethylsilyl-3-n-propylindene
(XX)
1-Trimethylsilyl-2,3-dimethylindene (XII, 2.0 g,
0.0092 mol) in CH2Cl2 (50 ml) was added dropwise via
syringe to a solution of TiCl4 (1.1 ml, 0.01 mol) in
CH2Cl2 and stirred overnight producing a burgundy
colored solution. The solvent, chlorotrimethyl-silane,
and excess TiCl4 were removed under vacuum and the
crude product residue washed with 50 ml of pentane.
The burgundy colored pentane solution was transferred
to a Schlenk flask via filter cannula and chilled to
−20°C to yield burgundy colored crystals. The remain-
ing residue was recrystallized from pentane–CH2Cl2
(10:1) to yield burgundy colored crystals for a total of
2.38 g (0.008 mol, 87% yield). 1H-NMR: (CDCl3) l
7.75–7.61 (m, 2H, arom.), 7.55–7.31 (m, 2H, arom.),
7.00 (s, 1H, 3-position), 2.66 (s, 3H, 1-position CH3),
2.56 (s, 3H, 2-position CH3). 13C-NMR (CDCl3): l
13.62 (1-position CH3), 16.82 (2-position CH3), 116.69
(3-position C), 125.93 (4-position C), 127.84 (7-position
C), 129.13 (5-position C), 129.24 (6-position C), 131.65
(9-position C), 131.75 (8-position C) 132.43 (1-position
C), 140.07 (2-position C). Anal. Found (%): C, 44.17;
H, 3.77. C11H11Cl3Ti Anal. Calc. (%): C, 44.42; H, 3.72.
The method of preparation was the same as for
1-trimethylsilyl-3-allylindene except butyllithium (8.0
ml, 1.6 M in hexane, 0.013 mol) was reacted with
1-n-propylindene (IX, 2.0 g, 0.013 mol), followed by
reaction with chlorotrimethylsilane (2.0 ml, 0.016 mol).
Work-up of the residue yielded 1-trimethylsilyl-3-
1
propylindene as a yellow oil. H-NMR (CDCl3): l 7.38
(m, 2H, arom.), 7.23 (m, 2H, arom.), 6.32 (s, 1H, sp2
2-position, J(2-1)=1.8 Hz), 3.18 (s, 1H, sp3 1-position,
J(1-2)=1.8 Hz), 2.14 (t, 2H, –CH2CH2CH3, J(1%-2%)=
2.2 Hz), 1.51 (m, 2H, –CH2CH2CH3, J(2%-1%)=2.2 Hz,
J(2%-3%)=3.2 Hz), 0.96 (t, 3H, –CH2CH2CH3, J(3%-
2%)=3.2 Hz), 0.01 (s, 9H, Si(CH3)3).
3.22. Synthesis of 1-trimethylsilyl-3-(4%
-but-1%-enyl)indene (XXI)
The method of preparation was the same as for
1-trimethylsilyl-3-allylindene except that butyllithium
(7.5 ml, 1.6 M in hexane, 0.012 mol) was reacted with
3-(4%-but-1%-enyl)indene (XI, 2.0 g, 0.012 mol), followed
by reaction with chlorotrimethylsilane (1.5 ml, 0.012
mol). Work-up of the residue yielded 1-trimethylsilyl-3-
(4%-but-1%-enyl)indene as a yellow oil.1H-NMR (CDCl3):
l 7.4–7.2 (m, 4H, arom.), 6.22 (bs, 1H, sp2 2-position),
5.95 (m, 1H, –CH2CH2CHꢀCH2, J(2%-1%trans)=8.2
Hz), 5.12 (d of m, 1H, –CH2CH2CHꢀCHH
trans, J(1%trans-2%)=8.2 Hz), 4.95 (m, 1H,
–CH2CH2CHꢀCHH cis), 3.42 (m, 1H, sp3 1-posi-
tion, J(1%-4%)=1.4 Hz), 2.8–2.4 (m of m, 4H,
3.25. Synthesis of 1,3-dimethylindenyltrichlorotitanium
(2) [15]
1-Trimethylsilyl-1,3-dimethylindene (XIII, 2.0 g,
0.0092 mol) in CH2Cl2 (50 ml) was added dropwise via
syringe to a solution of TiCl4 (1.1 ml, 0.01 mol) in
CH2Cl2 and stirred overnight producing a burgundy
colored solution. The solvent, chlorotrimethyl-silane,
and excess TiCl4 were removed under vacuum and the

T.E. Ready et al. / Journal of Organometallic Chemistry 583 (1999) 11–27
23
crude product residue washed with 50 ml of pentane.
3.28. Synthesis of 4,5,6,7-tetramethylindenyl-
trichlorotitanium (5)
The burgundy colored pentane solution was transferred
to a Schlenk flask via filter cannula and chilled to
−20°C to yield burgundy colored crystals. The remain-
ing residue was recrystallized from pentane–CH2Cl2
(10:1) to yield burgundy colored crystals for a total of
1.94 g (0.008 mol, 85% yield).1H-NMR: (CDCl3) l 7.76
(m, 2H, arom.), 7.57 (m, 2H, arom.), 6.81 (s, 1H,
2-postion), 2.78 (s, 6H, 1 and 3-position CH3). Anal.
Found (%): C, 43.61; H, 3.92. C11H11Cl3Ti Anal. Calc.:
C, 44.42; H, 3.72%.
1-Trimethylsilyl-4,5,6,7-tetramethylindene (XVI, 2.0
g, 0.0082 mol) in CH2Cl2 (50 ml) was added dropwise
via syringe to a solution of TiCl4 (1.1 ml, 0.01 mol) in
CH2Cl2 and stirred overnight producing a green colored
solution. The solvent, chlorotrimethylsilane, and excess
TiCl4 were removed under vacuum and the crude
product residue washed with 50 ml of pentane. The
purple colored pentane solution was transferred to a
Schlenk flask via filter cannula and chilled to −20°C to
yield purple colored crystals. The remaining residue was
recrystallized from pentane to yield purple colored crys-
tals for a total of 2.62 g (0.008 mol, 98% yield).
1H-NMR: (CDCl3) l 7.09 (d, 2H, 1 and 3-positions),
7.01 (t, 1H, 2-position), 2.53 (s, 6H, 4 and 7-position
CH3), 2.38 (s, 6H, 5 and 6-position CH3). Anal. Found
(%): C, 47.94; H, 4.43. C13H15Cl3Ti Anal Calc. (%): C,
47.97; H, 4.65.
3.26. Synthesis of 1,2,3-trimethylindenyl-
trichlorotitanium (3)
1-Trimethylsilyl-1,2,3-trimethylmethylindene (XIV,
2.0g, 0.0087 mol) in CH2Cl2 (50 ml) was added drop-
wise via syringe to a solution of TiCl4 (1.1 ml, 0.01 mol)
in CH2Cl2 and stirred overnight producing a green
colored solution. The solvent, chlorotrimethylsilane,
and excess TiCl4 were removed under vacuum and the
crude product residue washed with 50 ml of pentane.
The purple colored pentane solution was transferred to
a Schlenk flask via filter cannula and chilled to −20°C
to yield purple colored crystals. The remaining residue
was recrystallized from pentane to yield purple colored
crystals for a total of 2.57 g (0.008 mol, 94% yield).
1H-NMR: (CDCl3) l 7.83–7.65 (m, 2H, arom.), 7.60–
7.42 (m, 2H, arom.), 2.72 (s, 6H, 1 and 3-position CH3),
2.53 (s, 3H, 2-postion CH3). 13C-NMR (CDCl3): l
14.32 (1 and 3-position CH3), 14.59 (2-position CH3),
126.14 (4 and 7-position C), 128.72 (5 and 6-position
C), 131.27 (8 and 9-position C), 132.07 (1 and 3-posi-
tion C), 138.51 (2-position C). Anal. Found (%): C,
46.13; H, 4.01. C12H13Cl3Ti Anal. Calc. (%): C, 46.27;
H, 4.21.
3.29. Synthesis of 1,2,4,5,6,7-hexamethyltrichloro-
titanium (6)
1-Trimethylsilyl-2,3,4,5,6,7-hexamethylindene (XVII,
1.0 g, 0.0037 mol) in CH2Cl2 (50 ml) was added drop-
wise via syringe to a solution of TiCl4 (1.1 ml, 0.01 mol)
in CH2Cl2 and stirred overnight producing a green
colored solution. The solvent, chlorotrimethylsilane,
and excess TiCl4 were removed under vacuum and the
crude product residue washed with 50 ml of pentane.
The purple colored pentane solution was transferred to
a Schlenk flask via filter cannula and chilled to −20°C
to yield purple colored crystals. The remaining residue
was recrystallized from pentane to yield purple colored
crystals for a total of 0.983 g (0.0028 mol, 75% yield).
1H-NMR: (CDCl3) l 6.90 (s, 1H, 3-position), 2.86 (s,
3H, 1-position CH3), 2.68 (s, 3H, 2-position CH3), 2.53
(s, 3H, 7-position CH3), 2.47 (s, 3H, 4-position CH3),
2.38 (s, 3H, 6-position CH3), 2.35 (s, 3H, 5-position
CH3). Anal. Found (%): C, 51.31; H, 5.73. C15H19Cl3Ti
Anal. Calc. (%): C, 50.96; H, 5.42.
3.27. Synthesis of 1,3,4,7-tetramethylindenyltrichloro-
titanium (4)
1-Trimethylsilyl-1,3,4,7-tetramethylindene (XV, 2.0 g,
0.0082 mol) in CH2Cl2 (50 ml) was added dropwise via
syringe to a solution of TiCl4 (1.1 ml, 0.01 mol) in CH2Cl2
and stirred overnight producing a green colored solution.
The solvent, chlorotrimethylsilane, and excess TiCl4 were
removed under vacuum and the crude product residue
washed with 50 ml of pentane. The purple colored
pentane solution was transferred to a Schlenk flask via
filter cannula and chilled to −20°C to yield purple
colored crystals. The remaining residue was recrystallized
from pentane to yield purple colored crystals for a total
3.30. Synthesis of 1,2,3,4,5,6,7-heptamethylindenyl-
trichlorotitanium (7) [4f ]
1-Trimethylsilyl-1,2,3,4,5,6,7-heptamethylindene
(XVIII, 2.0 g, 0.0070 mol) in CH2Cl2 (50 ml) was added
dropwise via syringe to a solution of TiCl4 (1.1 ml, 0.01
mol) in CH2Cl2 and stirred overnight producing a green
colored solution. The solvent, chlorotrimethylsilane,
and excess TiCl4 were removed under vacuum and the
crude product residue washed with 50 ml of pentane.
The green colored pentane solution was transferred to a
Schlenk flask via filter cannula and chilled to −20°C to
1
of 2.22 g (0.0068 mol, 83% yield). H-NMR: (CDCl3) l
7.05 (s, 2H, 5 and 6-positions), 6.65 (s, 1H, 2-position),
2.91 (s, 6H, 1 and 3-position CH3), 2.70 (s, 6H, 4 and
7-position CH3). Anal. Found (%): C, 48.30; H, 4.86.
C13H15Cl3Ti Anal. Calc. (%): C, 47.96; H, 4.64.

24
T.E. Ready et al. / Journal of Organometallic Chemistry 583 (1999) 11–27
yield green colored crystals. The remaining residue
was recrystallized from pentane to yield green colored
crystals for a total of 2.08 g (0.0057 mol, 81% yield).
1H-NMR: (CDCl3) l 2.53 (s, 6H, 1 and 3-position
CH3), 2.49 (s, 3H, 2-position CH3), 2.37 (s, 6H, 4 and
7-position CH3), 2.36 (s, 6H, 5 and 6-position CH3).
Anal. Found (%): C, 52.75; H, 5.79. C16H21Cl3Ti
Anal. Calc. (%): C, 52.28; H, 5.76.
upon work-up afforded 8.79 g (97%) of dark red crys-
tals. H-NMR (CDCl3): l 7.80 (m, 2H, arom.), 7.52
1
(m, 2H, arom.), 7.13 (d, 1H, 3-position, J(3-2)=3.4
Hz), 6.97 (d, 1H, 2-position, J(2-3)=3.4 Hz), 5.85
(m, 1H, 2%-position, J(2%-3%)=8.8 Hz, J(2%-1%trans)=
3.6 Hz), 5.12 (dm, 1H, 1%-position trans, J(1%-
2%trans)=3.6 Hz, J(1%-1%gem)=1.3 Hz), 4.96 (m, 1H,
1%-position cis, J(1%-1%gem)=1.3 Hz), 3.27 (t, 2H, 4%-
position, J(4%-3%)=8.9 Hz), 2.51 (m, 2H, 3%-position,
J(3%-4%)=8.9 Hz, J(3%-2%)=8.8 Hz). Anal. Found (%):
C, 48.46; H, 3.64. C13H13Cl3Ti Anal. Calc. (%): C,
48.27; H, 4.05.
3.31. Synthesis of 1-allylindenyltrichlorotitanium (9)
TiCl4 (3.2 ml, 0.029 mol) was added via syringe to
100 ml of CH2Cl2 in a 250-ml side-armed Schlenk
flask that was fitted with a gas outlet valve connected
to a mercury overpressure bubbler. 1-Trimethylsilyl-3-
allylindene (XIX, 6.4 g, 0.028 mol) was then added
and the dark burgundy solution allowed to react
overnight at room temperature. After the solvent was
removed under vacuum, the burgundy residue was
washed with 50 ml of pentane and dried under vac-
uum. Recrystallization of the residue from pentane
3.34. Synthesis of 1-n-butylindenyltrichlorotitanium (12)
The method of preparation was the same as for
1-allylindenyltrichlorotitanium except that TiCl4 (3.2
ml, 0.029 mol) was reacted with 1-trimethylsily-3-
butyllindene (XXII, 6.6 g, 0.027 mol). Recrystalliza-
tion of the residue from a minimum volume of
CH2Cl2 afforded 8.09 g (92%) of dark red crystals.
1H-NMR (CDCl3): l 7.80 (m, 2H, arom.), 7.53 (m,
2H, arom.), 7.14 (d, 1H, 3-position, J(3-2)=3.3 Hz),
6.97 (d, 1H, 2-position, J(2-3)=3.3 Hz), 3.17 (t, 2H,
1%-position, J(1%-2%)=7.5 Hz), 1.72 (m, 2H, 2%-position,
J(2%-1%)=7.5 Hz, J(2%-3%)=7.4 Hz), 1.44 (m, 2H, 3%-
position, J(3%-4%)=11.9 Hz, J(3%-2%)=7.4 Hz), 0.98 (t,
3H, 4%-position, J(4%-3%)=11.9 Hz). Anal. Found (%):
C, 48.45; H, 4.76. C13H15Cl3Ti Anal. Calc. (%): C,
47.99; H, 4.65.
1
afforded 7.63 g (88% yield) of dark red crystals. H-
NMR (CDCl3): l 7.78 (m, 2H, arom.), 7.51 (m, 2H,
arom.), 7.15 (d, 1H, 3-position, J(3-2)=3.4 Hz), 6.97
(d, 1H, 2-position, J(2-3)=3.4 Hz), 6.04 (m, 1H, sp2,
–CH2CHꢀCH2, J(2%-3%)=5.8 Hz, J(2%-1%trans)=6.4
Hz) 5.27 (dm, 1H, sp2, –CH2CHꢀCH2 cis, J(1%-
1%gem)=1.8 Hz), 5.10 (dm, 1H, sp2, –CH2CHꢀCH2
trans, J(1%-2% trans)=6.4 Hz, J(1%-1%gem)=1.8 Hz),
3.93 (dm, 2H, sp3, –CH2CHꢀCH2, J(3%-2%)=5.8 Hz).
Anal. Found (%): C, 46.83; H, 3.68. C12H11Cl3Ti
Anal. Calc. (%): C, 46.57; H, 3.58.
3.35. Synthesis of indenyltrimethyltitanium (13)
3.32. Synthesis of 1-n-propylindenyltrichlorotitanium
(10)
Indenyltrichlorotitanium (5.0g, 0.0185 mol) was dis-
solved in 150 ml of diethyl ether and contained in a
250 ml side-armed round bottomed flask fitted with a
mercury overpressure bubbler and cooled to −78°C.
Methyllithium (39.6 ml, 1.4 M in ether, 0.0555 mol)
was added via syringe and the yellow colored solution
stirred for 2 h. After warming to 0°C, the ether was
removed by vacuum and replaced with 50 ml of cold
pentane. The slurry was stirred for 15 min while
maintaining the temperature at 0°C. The yellow col-
ored solution was filtered using a filter cannula and
stored at −20°C overnight. The supernatant mother
liquor was removed and the yellow colored crystals
were dried by blowing argon over them for 15 min
while maintaining a cold temperature. The crystals
were very temperature sensitive, turning to a white
The method of preparation was the same as for
1-allylindenyltrichlorotitanium except that TiCl4 (3.2
ml, 0.029 mol) was reacted 1-trimethylsilyl-3-propylin-
dene (XX, 5.75 g, 0.025 mol), which upon work-up
1
afforded 7.16 g (92%) of dark red crystals. H-NMR
(CDCl3): l 7.80 (m, 2H, arom.), 7.56 (m, 2H, arom.),
7.15 (d, 1H, 3-position, J(3-2)=3.0 Hz), 6.98 (d, 1H,
2-position, J(2-3)=3.0 Hz), 3.15 (t, 2H, 1%-position,
J(1%-2%)=8.2 Hz), 1.79 (m, 2H, 2%-position, J(2%-3%)=
7.3 Hz, J(2%-1%)=8.2 Hz), 1.04 (t, 3H, 3%-position,
J(3%-2%)=7.3 Hz). Anal. Found (%): C, 46.69; H,
4.35. C12H13Cl3Ti Anal. Calc. (%): C, 46.27; H, 4.21.
1
3.33. Synthesis of 1-(4%-but-1%-enyl)indenyltrichloro-
titanium (11)
powder at room temperature after an hour. H-NMR:
(C6D6) l 7.23 (m, 2H, 4 and 7-positions), 6.95 (m,
2H, 5 and 6 positions), 5.74 (d, 2H, 1 and 3-positions,
J(1,3-2)=3.2 Hz), 5.38 (t, 1H, 2-position, J(2-1,3)=
3.2 Hz), −0.50 (s, 9H, CH3). Anal. Found (%): C,
68.41; H, 5.89. C12H16Ti Anal. Calc. (%): C, 69.25; H,
7.75.
The method of preparation was the same as for
1-allylindenyltrichlorotitanium except that TiCl4 (3.2
ml, 0.029 mol) was reacted with 1-trimethylsilyl-3-(4%-
but-1%-enyl)indene (XXI, 6.8 g, 0.028 mol), which

T.E. Ready et al. / Journal of Organometallic Chemistry 583 (1999) 11–27
25
3.36. Synthesis of indenyldichloromethyltitanium (14)
CaH2), followed by an injection of 3.2 ml of 3.1 M
MAO, into 250 ml crown capped pressure bottles
sealed under inert atmosphere and brought to constant
50°C. At this time the solutions were stirred for 10 min
to scavenge impurities. Polymerizations were initiated
by injection of 0.5 ml of 5 mM titanium precursor
solution. Polymerization reactions were run for 30 min
and quenched by the addition of 100 ml of 10% HCL/
methanol. The resulting polymers were filtered, dried,
and weighed (for calculation of activity). The bulk
polymers were extracted using a Soxhlet extractor for
12 h in 2-butanone, dried, and weighed (for calculation
of the percentage syndiotactic polystyrene) [3a, 28, 29,
30].
Indenyltrichlorotitanium (5.0 g, 0.0185 mol) was dis-
solved in 150 ml of diethyl ether contained in a 250 ml
side-armed round bottomed flask fitted with a mercury
overpressure bubbler and cooled to −78°C. Methyl-
lithium (13.2 ml, 1.4 M in ether, 0.0185 mol) was added
via syringe and the yellow colored solution stirred for 2
h. After warming to 0°C, the ether was removed by
vacuum and replaced with 50 ml of cold pentane. The
slurry was stirred for 15 min while maintaining the
temperature at 0°C. The cold orange solution was
filtered using a filter cannula and stored at −20°C
overnight. The supernatant mother liquor was removed
and the orange colored crystals were dried under vac-
uum. The total yield from the mother liquor was 4.38 g
(95%). 1H-NMR: (C6D6) l 7.38 (m, 2H, 4 and 7
positions), 7.08 (m, 2H, 5 and 6 positions), 6.55 (d, 2H,
1 and 3-positions, J(1,3-2)=7.1 Hz), 6.30 (t, 1H, 2-po-
sition, J(2-1,3)=7.1 Hz), 1.75 (s, 3H, CH3). Anal.
Found (%): C, 47.62; H, 4.25. C10H10Cl2Ti Anal. Calc.
(%): C, 48.24; H, 4.05.
3.39. Ethylene polymerizations
Polymerizations of ethylene using the various catalyst
precursors were carried out by injecting 46.8 ml of
toluene followed by injection of 3.2 ml of 3.1 M MAO
into 250 ml crown capped pressure bottles sealed under
inert atmosphere and brought to constant polymeriza-
tion temperature. At this time the solutions were stirred
for 10 min to scavenge impurities. The pressure bottle
was degassed via vacuum followed by pressurization
with ethylene (15 psig) and the system allowed to
equilibrate for 20 min. The degassing/pressurization
procedure was repeated twice more. Polymerizations
were initiated by the injection of 0.5 ml of 5 mM
titanium precursor solution. Polymerization reactions
were run for 2 h and quenched by the addition of 100
ml of 10% HCL/methanol. The resulting polymers were
filtered, dried, and weighed (for calculation of activity).
3.37. Synthesis of (p5-indenyl)(p7-cyclo-
heptatrienyl)titanium (15) [17]
Cycloheptatriene (1.0 ml, 0.0096 mol) was added to
Mg turnings (3.65 g, 0.15 mol) in 100 ml of THF
contained in a 300 ml side-armed flask equipped with a
magnetic stirrer and a gas outlet valve connected to a
Hg over pressure bubbler, and the mixture stirred for
15 min. IndTiCl3 (2.0 g, 0.0074 mol) in 100 ml of THF
was added to the flask and stirred for approximately 30
min during which time the color of the reaction mixture
turned from orange to black. The THF was removed
under reduced pressure, replaced with 200 ml of
toluene, and stirred vigorously for 15 min. The reaction
mixture was filtered over a 5 cm silica plug which had
been previously washed with toluene, to yield a bright
green solution. The green solution was concentrated
and chilled to −20°C after which green crystals crys-
tals of IndTi(C7H7) formed (total yield=0.46 g, 0.0018
mol, 24%). The product can also be purified by vacuum
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26
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established either by 13C-NMR [3a] or by the melting tempera-

T.E. Ready et al. / Journal of Organometallic Chemistry 583 (1999) 11–27
27
ture (Tm) of the polymer; Tm(s-PS)/270°C, Tm(i-PS)/240°C [30].
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