Linear or cross-shaped di(cyclopentadienyltitanium) compounds with aryl or heteroaryl spacers

Article abstract of DOI:10.1039/c0dt01060j

The preparation of hexamethylated and hexabenzylated arylene or heteroarylene bridged dinuclear di(cyclopentadienyltitanium) compounds from the reaction of the corresponding hexachlorides with methyllithium or benzylmagnesium chloride is described. The spacers between the cyclopentadienyl rings consist of one, two or three phenylene groups, a dioctyloxyphenylene group or a 2,2′-bithienylene group. The corresponding hexachlorides and hexaisopropoxides have also been prepared.

Full text of DOI:10.1039/c0dt01060j

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PAPER
Linear or cross-shaped di(cyclopentadienyltitanium) compounds with aryl or
heteroaryl spacers†
Sana Ahmad, Suvendu Sekhar Dey, Bernard Jousseaume* and Thierry Toupance
Received 18th August 2010, Accepted 28th September 2010
DOI: 10.1039/c0dt01060j
The preparation of hexamethylated and hexabenzylated arylene or heteroarylene bridged dinuclear
di(cyclopentadienyltitanium) compounds from the reaction of the corresponding hexachlorides with
methyllithium or benzylmagnesium chloride is described. The spacers between the cyclopentadienyl
rings consist of one, two or three phenylene groups, a dioctyloxyphenylene group or a 2,2¢-bithienylene
group. The corresponding hexachlorides and hexaisopropoxides have also been prepared.
consists of linking oxo-titanium clusters obtained by hydrolysis
of titanium tetraalkoxides to an organic network of in situ
Introduction
polymerized ligands such as unsaturated acids.7 In the second
approach, preformed oxo-titanium clusters containing eight metal
atoms are linked with difunctional phthalic acid.8 In the first case,
aggregation of clusters takes place leading to larger oxo-titanium
species.7c,7d,9
We report here our studies concerning the synthesis of suitable
precursors able to allow the preparation of a new type of titanium-
based hybrid materials where both networks are linked through
strong titanium–cyclopentadienyl bonds. These compounds are
di(polymethylcyclopentadienyltitanium) derivatives where the cy-
clopentadienyl groups are bounded by different spacers and
where the titanium atoms bear hydrolyzable groups. It was very
important to get spacers of different lengths in order to enable
the study of an eventual ordering in the corresponding materials.
The presence of various hydrolyzable groups was also important
to change the rates of hydrolysis of the precursors, one of the
factors acting upon the kinetics of the formation of the hybrid
materials.
In the past few years, hybrid materials have received particular
attention. These new materials, where organic and inorganic net-
works are linked through weak or strong bonds show interesting
properties in optics, electronics, membranes, coatings, etc.1 Class II
hybrid materials where the organic and the inorganic components
are connected through covalent bonds have been mainly developed
from silicon derivatives. These organometallic compounds show
strong metal–carbon bonds that resist acidic, basic or fluoride
catalyzed sol–gel conditions. Disilylated compounds where two
silicon atoms bearing three alkoxyl groups are linked by a spacer
proved to be excellent precursors of various types of microporous
or mesoporous silica.2 Moreover molecular engineering allowed
preparation of functionalized materials that are organized by self-
assembly3 or by the use of surfactants.4 Besides silicon-based
hybrid materials, tin-based hybrids materials with alkyl– and aryl–
tin bonds were recently described.5 As in the case of silicon, van der
Waals and p-stacking interactions were strong enough to organize
these materials. The presence of long alkyl chains grafted on the
main metal–metal chain allowed the building of a highly organized
monoclinic structure.6
Up to now, hybrid materials with metal–carbon bonds have been
limited to silicon and tin as metals. To the best of our knowledge
no example has been described with transition metals. In the case
of titanium, for instance, the s-titanium–carbon bonds are not
hydrolytically stable enough to allow the successful preparation
of materials based on oxygen–titanium–carbon linkages. The
titanium-based hybrid materials prepared up to now are based on
oxygen–titanium–oxygen–carbon bonding. Two main preparative
approaches have been used for their syntheses. The first one
Results and discussion
To get precursors with the requisite properties, we focused first
on bis(tetramethylcyclopentadienyl) compounds with aromatic
spacers. Aromatic spacers were selected because (1) they were
expected to lead to ligands more easily prepared than ligands
with aliphatic spacers, (2) they are not prone to give disubsti-
tution of titanium compounds, and (3) they would give ligands
with high self-assembly capacity by p-stacking interactions. We
chose to substitute the cyclopentadienyl groups with methyl
substituents to get more stable ligand–metal bonds. The syn-
thesis of such compounds is well documented. It starts with
the condensation of a bimetallic species, Grignard or lithium
reagents, with tetramethylcyclopentenone, followed by dehydra-
tion of the formed diol. Then, to introduce the metal atoms, the
Universite´ de Bordeaux, CNRS, UMR 5255; ISM; Mate´riaux, 351 cours
de la Libe´ration, 33405, Talence, France. E-mail: b.jousseaume@ism.
u-bordeaux1.fr
† Electronic supplementary information (ESI) available: Full synthesis and
characterization for 3a–7a and 8–11. See DOI: 10.1039/c0dt01060j
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dicyclopentadienyl lithium salts can react either with a trialkoxy-
chlorotitanium or could be transmetallated into a disilylated
compound, as was shown for monometallic compounds,10 that
allows a smooth reaction with titanium tetrachloride avoiding a
secondary reduction into titanium(III) species. As in some cases
the disilylation of bis(tetramethylcyclopentadienyl) compounds
did not lead us to satisfactory yields of disilylated derivatives,
we turned to the procedure using a trialkoxychlorotitanium
described by Do et al.11 This procedure has also the advantage
of avoiding the formation of monosubstitution compound,12
4-(tetramethylcyclopentadienyl)biphenyl, a by-product in the
preparation of 4,4¢-bis(tetramethylcyclopentadienyl)biphenyl.
This method was successfully extended to 1c with a pheny-
lene group, to 3c with a triphenylene group and to 4b bear-
ing only two methyl groups on the cyclopentadienyl groups.
It was modified by the use of dichlorodimethylsilane in-
stead of chlorotrimethylsilane to get a faster chlorination step
(Scheme 1).
The octyloxyl substituted complexes were prepared in the
same manner as the unsubstituted ones. The dimetallation
of 2,5-dibromo-1,4-dioctyloxybenzene with t-butyllithium in di-
ethylether furnished a dilithiated derivative which was then
condensed with 2,3,4,5-tetramethycyclopentenone. In this case,
however, the expected diol was not obtained perhaps due to steric
hindrance of the long alkyl chains. In order to reduce the steric
hindrance and to ease the attack of the dilithiated derivative on
the ketone, the 2,3,4,5-tetramethylcyclopentenone was replaced by
3,4-dimethycyclopentenone. The required diol was then obtained
in good yield. It was not purified and was subsequently dehydrated
at room temperature by treatment with a catalytic amount of p-
toluenesulfonic acid. Recrystallization in toluene gave the dicy-
clopentadienyl ligand in good yield. Its treatment with two equiv-
alents of n-butyllithium led to the corresponding dilithiated deriva-
tive as a white powder that was metallated with a stoichiometric
amount of chlorotriisopropoxytitanium. The coupling was more
difficult than with laterally unsubstituted spacers. The expected
product was recovered in satisfactory yield only after refluxing for
4 days. Washing the unreacted chlorotriisopropoxytitanium with
pentane led to the sensitive hexaisopropoxydititanium 5b with a
cross-shaped spacer. It was chlorinated to give 5c as shining violet
crystals.
Precursors with a bithienylene spacer were then prepared
as this spacer should potentially increase stacking interac-
tions between the ligands by sulfur–sulfur interactions. A
bis(tetramethylcyclopentadienyl) ligand with a thienylene spacer
was reported recently and used in germanium, tin13 and iron
chemistry.14 It was obtained in low yield (10%) by a two-step
procedure involving a monocyclopentadienyl substituted inter-
mediate. The one-step procedure described above that involves
in this case the addition of 5,5¢-dilithio-2,2¢-bithiophene15 on
2,3,4,5-tetramethylcyclopentenone led to the required new ligand
in higher yields (49%). Successive di-titanation and chlorination
of the metal atoms were achieved by reaction with chlorotriiso-
propoxytitanium and dichlorodimethylsilane, respectively, to give
6c as shining violet crystals.
Scheme 1 Synthesis of complexes 1–6.
Subsequent methylation18 of 1c, 2c, 3c, 5c and 6c with a
slight excess of methyllithium in diethyl ether at -78 ◦C for
2 h and then at room temperature for 1 h followed by evapo-
ration of the solvent, extraction with toluene, filtration on dry
Celite and evaporation of toluene, afforded the corresponding
hexamethylated derivatives 1d, 2d, 3d, 5d and 6d as yellow-green
microcrystalline powders in satisfactory yields. Evaporation of
toluene was conducted at temperature below 35 ◦C in order to
limit an extensive decomposition of the alkylated complexes. They
were purified by recrystallization from pentane. They looked to
be more oxygen, moisture and heat sensitive than the analogous
As was shown for other dinuclear compounds with aromatic
spacers16 not involved in cyclic frameworks,17 we assume that the
two TiX3 moieties have an anti-orientation with respect to the
spacer.
458 | Dalton Trans., 2011, 40, 457–462
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Fig. 1 1H (top) and 13C (bottom) NMR spectra of 6d.
cyclopentadienyltrimethyltitaniums and had to be manipulated
while shaded from light at room temperature. Benzylation of
2c and 3c was performed analogously with benzylmagnesium
chloride instead of methyllithium. Although alkylated compounds
were too sensitive to be shipped for microanalysis, fresh solutions
in C6D6 or CDCl3 were found quite pure by NMR as it is shown
in Fig. 1 for 6d.
To get reference compounds for spectroscopic studies on
the materials derived from the above described precursors, we
needed monomeric titanium oxides with a phenyltetramethyl-
cyclopentadienyl ligand. They were obtained by hydrolysis of
trimethyl(phenyltetramethylcyclopentadienyl)titanium by an im-
provement of the procedure which was described for a pen-
tamethylcyclopentadienyl compound (Scheme 2).19
The trichloride 8 was obtained more rapidly and in better
yield than described20 by using the more reactive (phenylte-
tramethylcyclopentadienyl)dimethylsilane 7 instead of the cor-
responding trimethylsilane. At -60 ◦C in chloroform, the
1H NMR spectrum of 7 indicates that it is a 78/22 mix-
ture of two silanes that isomerize at room temperature by
a rapid intramolecular sigmatropic rearrangement.21 Then the
trichloride was alkylated with methyllithium18 to give the new
trimethyl(phenyltetramethylcyclopentadienyl)titanium. Its partial
hydrolysis under water vapour led to the tetramethylated oxide
Scheme 2 Synthesis of complexes 10 and 11.
10 in high yield. When an excess of water was used, the 1H
NMR spectrum of the crude mixture showed that 11 was
mainly formed together with some uncharacterized oligomers.
However, the isolated yield was about three times higher than
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previously reported from the triethylamine-catalyzed hydrolysis
of the trichloride 8.20
8.3 Hz, CH), 7.67 (4H, s, CH); dC: 11.5, 12.5, 26.5, 75.6, 121.8,
122.0, 124.0, 126.1, 127.4, 131.3, 135.3, 138.1, 139.9.
4,4¢¢-Terphenylenebis(3,4-dimethylcyclopentadienyl)di(triisopro-
poxytitanium) (4b). The same procedure was followed as
for 1b except that 4,4¢¢-bis(3,4-dimethylcyclopentadienyl)
terphenyl (4a) was used instead of 1,4-bis(2,3,4,5-tetra-
methylcyclopentadienyl)benzene (1a). (Yield 42%) NMR
(CDCl3) dH: 1.02 (36H, d, 3JH–H = 6.1 Hz, Me), 2.14 (12H, s, Me),
4.46 (6H, m, JH–H = 6.1 Hz, CH), 6.39 (4H, s, CH) 7.61 (8H,
s, CH), 7.70 (4H, s, CH); dC: 13.38, 26.19, 76.98, 109.66, 126.0,
126.9, 127.3, 134.6, 138.3, 139.8.
Conclusions
In summary, new hexaalkylditaniums suitable for the preparation
of hybrid materials have been obtained from the alkylation of the
corresponding hexachlorides. Various spacers with one, two or
three benzene rings, or a bithienylene group were used. An im-
proved synthesis of (phenyltetramethylcyclopentadienyl)titanium
oxides, dimer or tetramer, has also been presented.
3
1,4-Dioctyloxyphenylene-2,5-bis(3,4-dimethylcyclopentadienyl)-
di(triisopropoxytitanium) (5b). The same procedure was followed
as for 1b except that 2,5-bis(3,4-dimethylcyclopentadienyl)-1,4-
dioctyloxybenzene (5a) was used instead of 1,4-bis(2,3,4,5-
tetramethylcyclopentadienyl)benzene (1a) and the reaction
mixture was refluxed for 4 days. Yield: 95%. Anal. Calcd. for
C54H94Ti2O8: C, 67.06; H, 9.80. Found: C, 66.42; H, 9.79. NMR
Experimental
General procedures
All reactions were carried out under a nitrogen atmosphere.
Pentane, THF, toluene and diethyl ether were distilled from
sodium benzophenone ketyl prior to use. Acetonitrile and
dichloromethane were distilled over CaH2. 1H, and 13C NMR
spectra were recorded on Bruker DPX 200, AC 250 or DPX
300 spectrometers. Elemental analyses were performed by
the “Service d’analyse du CNRS” at Vernaison, France.
1,4-Bis(tetramethylcyclopentadienyl)benzene (1a),22 4,4¢-bis-
(tetramethylcyclopentadienyl)biphenyl (2a),11 4,4¢-biphenylene-
bis(2,3,4,5-tetramethylcyclopentadienyl)di(triisopropoxytitanium)
(2b)11 and 4,4¢-biphenylenebis(2,3,4,5-tetramethylcyclopenta-
dienyl)di(titanium trichloride) (2c)11 were synthesized via a
literature procedure.
(CDCl3) dH: 0.87 (6H, t, 3JH–H = 6.5 Hz, Me), 1.03 (36H, d, 3JH–H
=
6.1 Hz, Me), 1.21–1.89 (24H, m, CH2), 2.12 (12H, s, Me), 3.99
(4H, t, 3JH–H = 6.5 Hz, CH2O), 4.50 (6H, m, 3JH–H = 6.1 Hz, CH),
6.56 (4H, s, CH), 7.11 (2H, s, CH); dC: 13.3, 14.3, 22.9, 26.2, 26.5,
29.5, 29.6, 29.8, 32.0, 69.4, 76.6, 112.7, 113.0, 121.1, 122.8, 125.1,
150.3.
5,5¢-Bithienylenebis(2,3,4,5-tetramethylcyclopentadienyl)di(trii-
sopropoxytitanium)
(6b). The
same
procedure
was
followed as for (1b) except that 5,5¢-bis(2,3,4,5-tetra-
methylcyclopentadienyl)bithiophene (6a) was used instead
of 1,4-bis(2,3,4,5-tetramethylcyclopentadienyl)benzene (1a) and
the reaction mixture was refluxed for 2 days. Yield: 40%. Anal.
Calcd. for C44H70S2Ti2O6: C, 61.82; H, 8.25. Found: C, 61.17; H,
Syntheses
1,4-Phenylenebis(2,3,4,5-tetramethylcyclopentadienyl)di(triiso-
propoxytitanium) (1b). In a dry Schlenk tube under nitro-
gen, a solution of n-BuLi (7.19 mL, 17.98 mol L-1) in pen-
tane was added dropwise to a solution of 1,4-bis(2,3,4,5-
tetramethylcyclopentadienyl)benzene (1a) (2.86 g, 8.99 mmol) in
3
7.96. NMR (CDCl3) dH: 1.11 (36H, d, JH–H = 6.0 Hz, Me), 2.06
(12H, s, Me), 2.20 (12H, s, Me), 4.58 (6H, m, 3JH–H = 6.0 Hz, CH),
3
3
6.91 (2H, d, JH–H = 3.8 Hz, CH), 7.11 (2H, d, JH–H = 3.8 Hz,
CH); dC: 11.5, 12.7, 26.5, 75.8, 116.4, 122.2, 122.4, 122.6, 127.9,
136.4, 136.9.
◦
THF (50 mL) at 0 C. The reaction mixture was stirred at room
temperature overnight. A solution of chlorotriisopropoxytitanium
(4.68 g, 17.99 mmol) in THF (30 mL) was added to the reaction
mixture at 0 ◦C and the resulting mixture was refluxed for
3 days. The solvent was evaporated under vacuum and the residue
was extracted with pentane. A yellow solid was obtained after
evaporation of the solvent which was then washed 3 times with
pentane to give the required product. Yield: 67%. Anal. Calcd. for
C42H70Ti2O6: C, 65.79; H, 9.20. Found: C, 65.27; H, 9.69. NMR
(CDCl3) dH: 1.06 (36H, d, 3JH–H = 6.1 Hz, Me), 2.06 (12H, s, Me),
2.12 (12H, s, Me), 4.48 (6H, m, 3JH–H = 6.1 Hz, CH), 7.36 (4H, s,
CH); dC: 11.5, 12.5, 26.5, 75.4, 121.7, 122.1, 124.6, 130.0, 133.4.
1,4-Phenylenebis(2,3,4,5-tetramethylcyclopentadienyl)di(titani-
um trichloride) (1c). In
trogen, chlorotrimethylsilane (5.09 g, 46.99 mmol) was
added slowly to solution of 1,4-phenylenebis(2,3,4,5-
a dry Schlenk tube under ni-
a
tetramethylcyclopentadienyl)di(triisopropoxytitanium) (1b) (2 g,
2.61 mmol) in dichloromethane (20 mL) at 0 ◦C. The reaction
mixture was stirred at room temperature for 24 h. A slow formation
of red precipitates was observed. The precipitates were allowed to
settle down and the solvent was decanted off. The red compound
was washed several times with acetonitrile and dried in vacuum.
The required product was obtained as red crystals. Due to very
low solubility of the compound in CDCl3 and other solvents, it
was not possible to obtain a good 13C NMR. Yield: 84%. Anal.
Calcd. for C24H28Ti2Cl6: C, 46.13; H, 4.51. Found: C, 45.59; H,
4.56. NMR (CDCl3) dH: 2.45 (12H, s, Me), 2.52 (12H, s, Me), 7.47
(4H, s, CH).
4,4¢¢ - Terphenylenebis(2,3,4,5 - tetramethylcyclopentadienyl)di-
(triisopropoxytitanium) (3b). The same procedure was
followed as for 1b except that 4,4¢¢-bis(2,3,4,5-tetra-
methylcyclopentadienyl)terphenyl (3a) was used instead of
1,4-bis(2,3,4,5-tetramethylcyclopentadienyl)benzene (1a). Yield:
68%. Anal. Calcd. for C54H78Ti2O6: C, 70.58; H, 8.55. Found: C,
4,4¢¢ - Terphenylenebis ( 2,3,4,5 - tetramethylcyclopentadienyl ) di-
(titanium trichloride) (3c). The same procedure was followed as
for 1c except that 3b was used instead of 1b. Yield: 87%. Anal.
Calcd. for C36H36Ti2Cl6: C, 55.64; H, 4.67. Found: C, 55.32; H,
3
70.94; H, 8.73. NMR (CDCl3) dH: 1.00 (36H, d, JH–H = 6.1 Hz,
Me), 1.99 (12H, s, Me), 2.06 (12H, s, Me), 4.43 (6H, m, 3JH–H = 6.1
3
3
Hz, CH), 7.40 (4H, d, JH–H = 8.3 Hz, CH), 7.58 (4H, d, JH–H
=
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4.92. NMR (CDCl3) dH: 2.46 (12H, s, Me), 2.54 (12H, s, Me), 7.47
(4H, s, CH), 6.95 (2H, s, CH); dC: d 14.1, 14.4, 23.2, 29.9, 30.0,
32.4, 62.3, 68.9, 111.7, 112.0, 122.8, 124.5, 125.1, 149.6.
3
3
(4H, d, JH–H = 8.3 Hz, CH), 7.73 (4H, d, JH–H = 8.3 Hz, CH),
7.75 (4H, s, CH); dC: 14.9, 15.8, 127.1, 127.8, 131.1, 132.4, 136.4,
139.0, 139.7, 140.9, 142.5.
5,5¢-Bithienylenebis(2,3,4,5-tetramethylcyclopentadienyl)di(tri-
methyltitanium) (6d). The same procedure was followed as for 1d
using 6c instead of 1c. Yield: 81%. NMR (CDCl3) dH: 0.94 (18H,
1,4-Dioctyloxy-2,5-phenylenebis(3,4-dimethylcyclopentadienyl)-
di(titanium trichloride) (5c). The same procedure was followed
as for 1c except that 5b was used instead of 1b and Me3SiCl
was replaced by Me2SiCl2. The reaction mixture was stirred
for 2 days at room temperature. Yield: 61%. Anal. Calcd. for
C36H52O2Ti2Cl6: C, 52.39; H, 6.35. Found: C, 53.68; H, 6.87.
s, Me), 2.00 (12H, s, Me), 2.18 (12H, s, Me), 6.78 (4H, d, 3JH–H
=
3.7 Hz, CH), 7.07 (4H, d, 3JH–H = 3.7 Hz, CH); dC: 12.4, 13.5, 64.4,
120.4, 121.7, 123.2, 124.4, 127.8, 129.2, 136.5.
4,4¢-Biphenylenebis(2,3,4,5-tetramethylcyclopentadienyl)di(trib-
enzyltitanium) (2e). The same procedure was followed as for 2d
using benzylmagnesium chloride instead of MeLi. The required
product was obtained as a red powder after the evaporation of the
solvent. Yield: 95%. NMR (CDCl3) dH: 1.96 (12H, s, Me), 2.03
(12H, s, Me), 2.81 (s, 12H, CH2Ph), 6.62–7.70 (38H, m, CH); dC:
12.4, 13.3, 96.7, 122.5, 122.7, 125.7, 126.8, 128.4, 128.6, 130.9,
134.2, 139.3, 139.8, 150.1.
3
NMR (CDCl3) dH: 0.87 (6H, t, JH–H = 6.5 Hz, Me), 1.30–1.99
3
(24H, m, CH2), 2.49 (12H, s, Me), 4.13 (4H, t, JH–H = 6.5 Hz,
CH2O), 7.29 (2H, s, CH), 7.40 (4H, s, CH); dC: 14.3, 16.2, 22.8,
26.5, 29.4, 29.5, 29.6, 32.0, 69.6, 113.0, 122.9, 124.3, 136.9, 139.3,
150.4.
5,5¢-Bithienylenebis(2,3,4,5-tetramethylcyclopentadienyl)di(tita-
nium trichloride) (6c). The same procedure was followed as for
1c except that 6b was used instead of 1b and Me3SiCl was replaced
by Me2SiCl2. Yield: 44%. Anal. Calcd. for C26H28S2Ti2Cl6: C,
43.79; H, 3.96. Found: C, 43.34; H, 3.67. NMR (CD2Cl2) dH: 2.42
(12H, s, Me), 2.64 (12H, s, Me), 7.22 (2H, d, 3JH–H = 3.8 Hz, CH),
7.30 (2H, d, 3JH–H = 3.8 Hz, CH).
4,4¢¢ - Terphenylenebis(2,3,4,5 - tetramethylcyclopentadienyl)di-
(tribenzyltitanium) (3e). The same procedure was followed as
for 2e using 3c instead of 2c. Yield: 92%. NMR (CDCl3) dH:
1.96 (12H, s, Me), 2.03 (12H, s, Me), 2.81 (s, 12H, CH2Ph),
6.62–7.72 (38H, m, CH), 7.78 (4H, s, CH); dC: 12.4, 13.4, 96.7,
122.5, 122.7, 125.7, 126.8, 127.6, 128.5, 130.9, 134.2, 139.3, 139.8,
150.1.
1,4-Phenylenebis(2,3,4,5-tetramethylcyclopentadienyl)di(trime-
thyltitanium) (1d). In
a dry Schlenk tube under nitro-
gen, covered with an aluminium foil, a solution of MeLi
(8.16 mL, 13.05 mmol) in diethyl ether was added slowly
Acknowledgements
Acknowledgement is made to the Aquitaine Region and the CNRS
(Material Program Grant) for partial financial support of this
work.
to
a solution of 1,4-phenylenebis(2,3,4,5-tetramethylcyclo-
pentadienyl)di(titanium trichloride) (1c) (1.36 g, 2.17 mmol) in
diethyl ether (30 mL) at -78 ◦C. The reaction mixture was stirred at
this temperature for 2 h and then at room temperature for 1 h. The
solvent was removed under vacuum and the residue was extracted
with toluene. The corresponding solution was then filtered on dry
Celite. The required product was obtained as a yellowish green
powder after the evaporation of the solvent at reduced temperature
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◦
(< 35 C) to avoid premature decomposition of the complex. It
was recrystallised in pentane. Yield: 62%. NMR (CDCl3) dH: 0.90
(18H, s, Me), 2.01 (12H, s, Me), 2.07 (12H, s, Me), 7.11 (4H, s,
CH); dC: 12.4, 13.3, 63.4, 120.3, 124.1, 129.7, 130.1, 134.1.
4,4¢ - Biphenylenebis(2,3,4,5 - tetramethylcyclopentadienyl)di(tri-
methyltitanium) (2d). The same procedure was followed as for 1d
using 2c instead of 1c. Yield: 71%. NMR (CDCl3) dH: 0.89 (18H,
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s, Me), 1.99 (12H, s, Me), 2.06 (12H, s, Me), 7.16 (4H, d, 3JH–H
=
8.1 Hz, CH), 7.55 (4H, d, 3JH–H = 8.1 Hz, CH); dC: 12.4, 13.2, 63.4,
120.3, 124.1, 126.5, 129.8, 130.7, 134.9, 138.8.
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4,4¢¢ - Terphenylenebis(2,3,4,5 - tetramethylcyclopentadienyl)di-
(trimethyltitanium) (3d). The same procedure was followed as
for 1d using 3c instead of 1c. Yield: 50%. NMR (CDCl3) dH: 0.94
(18H, s, Me), 2.03 (12H, s, Me), 2.11 (12H, s, Me), 7.22 (4H, d,
3JH–H = 8.3 Hz, CH), 7.63 (4H, d, 3JH–H = 8.3 Hz, CH), 7.71 (4H, s,
CH); dC: 12.4, 13.2, 63.5, 120.4, 124.2, 126.6, 127.5, 129.8, 130.8,
135.0, 138.9, 139.7.
1,4-Dioctyloxy-2,5-phenylenebis(3,4-dimethylcyclopentadienyl)-
di(trimethyltitanium) (5d). The same procedure was followed as
for 1d using 5c instead of 1c. Yield: 87%. NMR (CD2Cl2) dH: 0.89
(6H, t, 3JH–H = 6.5 Hz, Me), 0.90 (18H, s, Me), 1.31–1.85 (24H, m,
CH2), 2.06 (12H, s, Me), 3.94 (4H, t, 3JH–H = 6.5 Hz, CH2O), 6.63
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