Mono(cyclopentadienyl)titanium complexes containing a sulfide-bridged bis(phenolato) ligand. Molecular structure of Ti{2,2′-S(OC6H2-4-Me-6-tBu) 2}(η5-C5H5)Cl

Article abstract of DOI:10.1016/S0022-328X(00)00846-9

A series of titanium complexes containing a sulfur-bridged chelating bis(phenolato) ligand, Ti{2,2′-S(OC₆H₂-4-Me-6-^tBu) ₂}(η⁵-C₅R₅)Cl (R = H, Me; R₅ = 1,3-(SiMe₃)₂H₃), were prepared by the reaction of the dilithium derivative Li₂[2,2′-S(OC₆H₂-4-Me-6- ^tBu)₂] with Ti(η⁵-C₅R₅)Cl₃. Alkylation of the chloro complexes gave complexes of the type Ti{2,2′-S(OC₆H₂-4-Me-6-^tBu) ₂}-(η⁵-C₅R₅)R′ (R′ = Me, CH₂Ph). The crystal structure of the chloro complex Ti{2,2′-S(OC₆H₂-4-Me-6-^tBu) ₂}(η⁵-C₅H₅)Cl has been determined by X-ray diffraction and shows a monomeric four-legged piano-stool structure with the sulfur and chlorine atoms in trans positions. A long titanium-sulfur bond length of 2.907(1) A? was observed.

Full text of DOI:10.1016/S0022-328X(00)00846-9

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 621 (2001) 3–9
Mono(cyclopentadienyl)titanium complexes containing a
sulfide-bridged bis(phenolato) ligand. Molecular structure of
Ti{2,2%-S(OC6H2-4-Me-6-tBu)2}(h5-C5H5)Cl
Francisco Amor a, Stefan Fokken b, Thomas Kleinhenn b, Thomas P. Spaniol b,
Jun Okuda b,*
a Departamento de Qu´ımica Inorga´nica, Uni6ersidad de Alcala´, Campus Uni6ersitario, 28871 Alcala´ de Henares, Spain
b Institut fu¨r Anorganische Chemie und Analytische Chemie, Johannes Gutenberg-Uni6ersita¨t Mainz, Duesbergweg 10-14, 55099 Mainz, Germany
Received 25 August 2000; accepted 22 September 2000
Dedicated to Professor H. Brunner on the occasion of his 65th birthday
Abstract
A series of titanium complexes containing a sulfur-bridged chelating bis(phenolato) ligand, Ti{2,2%-S(OC6H2-4-Me-6-tBu)2}(h5-
C5R5)Cl (R=H, Me; R5=1,3-(SiMe3)2H3), were prepared by the reaction of the dilithium derivative Li2[2,2%-S(OC6H2-4-Me-6-
tBu)2] with Ti(h5-C5R5)Cl3. Alkylation of the chloro complexes gave complexes of the type Ti{2,2%-S(OC6H2-4-Me-6-tBu)2}-
(h5-C5R5)R% (R%=Me, CH2Ph). The crystal structure of the chloro complex Ti{2,2%-S(OC6H2-4-Me-6-tBu)2}(h5-C5H5)Cl
has been determined by X-ray diffraction and shows a monomeric four-legged piano-stool structure with the sulfur and chlorine
,
atoms in trans positions. A long titanium–sulfur bond length of 2.907(1) A was observed. © 2001 Elsevier Science B.V.
All rights reserved.
Keywords: Titanium complexes; Sulfur donor; Cyclopentadienyl ligand; Phenolato ligand
1. Introduction
ligands of the general type 2,2%-Z(OC6H2-4-Me-6-tBu)
where the link Z between the two bulky phenolato
moieties is varied systematically [4]. In particular, the
sulfide bridged system tbmp (Z=S) is important as
ancillary ligand in olefin polymerization catalysis [5].
We report here the synthesis of several alkyl derivatives
of the Ti(tbmp) fragment.
Titanium(IV) half-sandwich complexes of the type
Ti(h5-C5R5)X3 (X=one-electron ligand) can in princi-
ple accommodate up to three two-electron ligands L [1].
The full 18-electron configuration is not very frequently
encountered, since various degrees of p-donation may
occur to attenuate the Lewis-acidity [2]. Alkoxo and
phenoxo ligands are particularly variable monoanionic
ligands in this respect and have found application as
controlling ligands in several instances [3]. We have
been interested in the use of linked bis(phenolato)
2. Results and discussion
As reported earlier [4b], the reaction between
cyclopentadienyl lithium and the dichloro titanium
complex
with
a
sulfide-linked
bis(phenolato)
ligand, [Ti(tbmp)Cl2]2 (tbmp=2,2%-thiobis(6-tert-butyl-
4-methylphenolato)), gives mono(cyclopentadienyl)-
titanium complexes Ti(tbmp)(h5-C5R5)Cl (R=H, 1;
R=Me, 4), as shown in Eq. (1).
* Corresponding author. Tel.: +49-6131-3923737/25333; fax: +
49-6131-3925606.
E-mail address: okuda@mail.uni-mainz.de (J. Okuda).
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(00)00846-9

4
F. Amor et al. / Journal of Organometallic Chemistry 621 (2001) 3–9
(1)
These complexes, together with the new derivative
molecular structure of 1 and Table 1 summarizes se-
lected bond distances and angles.
Ti(tbmp){h5-1,3-(SiMe3)2C5H3}Cl (6), are also accessi-
ble from the metathesis reaction between the appropri-
ate trichloro titanium derivatives Ti(h5-C5R5)Cl3
(R=H, Me; R5=1,3-(SiMe3)2H3) and the dilithium or
disodium salts of the tbmp ligand in approximately the
same yields as via the previously reported method (Eq.
(2)). These reactions can be carried out in separate steps
or as a one-pot reaction with no significant differences
in the yields. The chloro derivatives are obtained as red
crystals which are soluble in ethers and slightly soluble
in aliphatic hydrocarbons.
Complex 1 crystallized with diethyl ether in the unit
cell. The coordination sphere around the titanium cen-
ter in 1 can be described as that of a four-legged
piano-stool in which the chlorine atom is located in
trans-position to the sulfur atom. The angles O–Ti–S
and O–Ti–Cl range from 70.42(5) to 95.08(6)° with a
sum of 328.51°. The titanium–sulfur bond length of
,
2.907(1) A is one of the largest so far reported in the
literature [4b,6], although it is still smaller than the sum
(2)
1
The H-NMR spectra of the complexes 1, 4 and 6
show one singlet for all the equivalent methyl groups of
the tert-butyl substituents on the phenyl rings and one
singlet for the two methyl substituents on the phenyl
rings, while the protons of the phenyl ring at position 3
and 5 appear as two doublets (4JHH ca. 2 Hz). The
signals for the protons, methyl and trimethylsilyl sub-
stituents on the cyclopentadienyl rings are observed in
the expected region. Based on similar mass spectral as
of the van der Waals radii of the two atoms [7].
This may suggest a weaker interaction between the
sulfur atom and the metal center than those reported
for other titanium–thioether complexes adducts
as
Ti(h5-C5H5)(SCH2CH2SCH2CH2S)
(2.600(1)
,
,
A) [8a], TiCl4(HSC6H11)2 (av. 2.664 A) [8b],
[Ti(h5-C5H5)(SCH2CH2S)Cl]2 (av. 2.513 A) [8c],
,
t
,
Ti(N Bu)Cl2(9-aneS3) (av. 2.638 A) [8d] and cis-
1
well as H- and 13C-NMR spectroscopic data of 4 and
,
TiCl4(S(CH2)4)2 (av. 2.265 A) [8e]. The tbmp ligand
6 to those of the parent complex 1, a structure
analogous to that of crystallographically characterized
1 can be implied for both compounds1. Crystals of 1
suitable for single-crystal X-ray diffraction were ob-
tained by slow crystallization from a diethyl ether/hex-
ane mixture. Fig. 1 shows an ORTEP plot of the
1 The X-ray diffraction study on a single crystal of 6 shows a
structure similar to that of 1 with a position for the chlorine atom
trans to the sulfur atom. Red crystal, 0.13×0.53×0.63 mm3, a=
,
9.484(2), b=20.623(6), c=18.680(3) A, h=k=90°, i=99.86(2)°,
3
,
V=3600(1) A , tentative space group P21/c. The poor quality of the
crystallographic data preclude further discussion of the results.

F. Amor et al. / Journal of Organometallic Chemistry 621 (2001) 3–9
5
Fig. 2. View of the eight-membered ring conformation in
Fig. 1. ORTEP diagram of the molecular structure of Ti(tbmp)(h5-
C5H5)Cl (1). Thermal ellipsoids are drawn at 50% probability level.
Hydrogen atoms are omitted for the sake of clarity. The Et2O solvent
molecule is also excluded.
Ti(tbmp)(h5-C5H5)Cl (1).
t
,
1.751 A in Ti{2,2%-CH2(OC6H2-4-Me-6- Bu)2}Cl2 [11a],
t
,
av. 1.776 A in Ti{2,2%-CH2(OC6H2-4-Me-6- Bu)2}(BH4)2
,
Table 1
[11b], av. 1.788 A in Ti{2,2%-CH2(OC6H2-4-Me-6-
5
tBu)2}(o-CH2NMe2C6H4)(OSO2CF3) [11d], and av. 1.81
,
Selected bond lengths (A) and bond angles (°) for Ti(tbmp)(h –
C5H5)Cl (1)
t
,
A in Ti{2,2%-(OC6H2-4-OMe-6- Bu)2}(CH2Ph)2 [12]).
Values larger than those found for titanium complexes
Bond lengths
Bond angles
with a non-linked alkoxo ligand as Ti(OC6H3-2,6-
t
,
TiꢀCl
TiꢀS
2.318(1)
2.907(1)
1.827(2)
1.827(2)
2.379(3)
2.380(3)
2.373(3)
2.349(3)
2.354(4)
1.769(2)
1.773(2)
1.344(2)
1.349(3)
ClꢀTiꢀO(1)
ClꢀTiꢀO(2)
SꢀTiꢀO(1)
SꢀTiꢀO(2)
SꢀTiꢀCl
O(1)ꢀTiꢀO(2)
TiꢀO(1)ꢀC(1)
TiꢀO(2)ꢀC(13)
C(2)ꢀSꢀC(12)
TiꢀSꢀC(2)
92.50(6)
95.08(6)
70.42(5)
70.51(6)
148.23(3)
115.59(8)
141.9(1)
137.8(1)
107.3 (1)
91.93(7)
89.93(8)
Bu2)Cl3(THF)2 (1.807(8) A) [9], Ti(OPh)2Cl2 (1.744(10)
,
,
A) [13a], Ti(OC6H3-2,6-Ph2)2Cl2 (1.726(2) A) [13b],
[Ti(OC6H3-2,6-Ph2)2]2(h-Cl)2 (av. 1.817 A) [13c],
Ti(OC6H3-2,6-Me2)2Cl2(THF)2 (av. 1.788 A) [13d], and
Ti(OC6H3-2,6- Pr2)(h -C5H5)(SPh)Cl (1.80(2) A) [13e]
may suggest a decrease in the p-donation from the
oxygen atoms to the metal center [14].
TiꢀO(1)
TiꢀO(2)
TiꢀC(23)
TiꢀC(24)
TiꢀC(25)
TiꢀC(26)
TiꢀC(27)
SꢀC(2)
,
,
i
5
,
Metathesis reactions of the chloro complexes 1, 4 and
6 with alkylating reagents MgMeCl or Mg(CH2Ph)Cl
resulted in the formation of alkyl complexes
Ti(tbmp)(h5-C5R5)R% (R=H, R%=Me (2), CH2Ph (3);
R=Me, R%=Me (5); R5=1,3-(SiMe3)2H3, R%=Me
(7), CH2Ph (8)) in moderate yields (68–75%) (Eq. (3)).
The complexes 2 and 5 are orange, the complexes 3 and
7 are dark yellow and the complex 8 is brown. They are
all soluble in aliphatic hydrocarbons. The reaction of
the chloro complex 4 with Mg(CH2Ph)Cl in THF at
−78°C results in the formation of a yellow reaction
mixture, but upon work-up the starting material was
recovered.
For the methyl complexes 2 and 7, the methyl group
at the titanium center are observed as singlets at 1.34
and 1.31 ppm, respectively, in the 1H-NMR spectra,
while for complex 5 the corresponding signal is high-
field shifted to 0.38 ppm. The 13C-NMR spectroscopic
TiCH3 resonances are observed at 58.1 for 2, 60.8 for 5,
and 60.5 ppm for 7. The benzyl derivatives 3 and 8
show only one resonance for the two equivalent methyl-
ene protons of the benzyl groups at 3.15 ppm and three
SꢀC(12)
O(1)ꢀC(1)
O(2)ꢀC(13)
TiꢀSꢀC(12)
adopts the typical boat conformation observed in other
complexes [4b,6] with the sulfur atom pointing towards
the metal center in the proximity of the cyclopentadi-
enyl ring (see Fig. 2). This is probably due to the
electron donating effect of the cyclopentadienyl ligand
and the steric hindrance of the tert-butyl groups. A
similar configuration is adopted by other related linked
bis(phenolato) ligands with a sulfinyl [4d], oxo [9],
tellurium [10] and methylene bridge [11]. The metal–
,
oxygen bond lengths of 1.827(2) A are in the expected
range for titanium complexes with a linked bis(pheno-
,
lato) ligand (av. 1.892 A in [Ti{2,2%-S(OC6H2-4-Me-6-
t
i
,
Bu)2}(O Pr)2]2 and av. 1.855 A in Ti{2,2%-S(OC6H2-4-
t
,
Me-6- Bu)2}(o-CH2NMe2C6H4)Cl [4b], av. 1.888 A in
Ti{2,2%-S(OC6H2-4-Me-6-tBu)2}Br2 [6], av. 1.872 A in
,
Ti{2,2%-Te(OC6H2-4-Me-6-tBu)2}(h5-C5Me5)Cl [10], av.

6
F. Amor et al. / Journal of Organometallic Chemistry 621 (2001) 3–9
broad signals for the protons of the benzylic phenyl
ring. The H-NMR spectra of the alkyl complexes 2, 3,
resonances and reported relative to tetramethylsilane.
Mass spectra were recorded on a Finnigan 8230 spec-
trometer. Elemental analyses were performed by the
microanalytical laboratory of this department.
1
5, 7 and 8 show patterns for the tbmp ligand similar to
1
those described for the H-NMR spectra of the chloro
precursors 1, 4 and 6: The methyl groups of the tert-bu-
tyl substituents on the phenolato groups remain equiva-
lent and appear in the region from 1.26 to 1.41 ppm
while the methyl substituents on the phenyl rings ap-
pear as a singlet at 2.2 ppm. The proton atoms on the
phenyl ring are recorded as doublets with a similar
coupling constant as in the chloro precursors.
3.1. Ti(tbmp)(p5-C5H5)Cl (1)
A solution of LinBu (2.1 ml of a 1.5 M solution in
THF) was added to a solution of tbmpH2 (1.1 g, 3.0
mmol) in hexane (ca. 25 ml) at 0°C and the mixture was
(3)
This work shows that the Ti(tbmp) fragment is stabi-
lized by a cyclopentadienyl ligand and alkylation of the
remaining chloro function becomes feasible. Previously,
we had encountered considerable difficulties in synthe-
sizing the ten-electron dialkyls of the type Ti(tbmp)R2
by alkylating the dichloro complex Ti(tbmp)Cl2 Such
problems do not appear in the preparation of the more
stable derivatives Ti(tbmp)(h5-C5R5)R% which formally
have a 14-valence electron configuration.
stirred for 16 h. The solvents were filtered off and the
white precipitate was washed with hexane (2×10 ml)
and dried in vacuo. A solution of Ti(h5-C5H5)Cl3 (0.50
g, 2.28 mmol) in diethyl ether (20 ml) was added to a
suspension of Li2(tbmp) (0.90 g, 2.4 mmol) in diethyl
ether (15 ml) at −78°C. The mixture was slowly
warmed up to room temperature (r.t.) and stirred for 16
h. Concentration of the solution followed by addition
of hexane (ca. 20 ml) and cooling to −30°C afford
1
0.92 g of dark red crystals (80%): H-NMR l 1.25 (s,
18H, 6-C(CH3)3), 2.21 (s, 6H, 4-CH3), 6.76 (s, 5H,
C5H5), 6.98 (d, 4JHH=1.6 Hz, 2H, 5-H), 7.27 (d,
4JHH=1.6 Hz, 2H, 3-H); 13C{1H}-NMR l 20.8 (4-
CH3), 29.8 (6-C(CH3)3), 35.2 (6-C(CH3)3), 119.4
(C5H5), 128.3 (C-2), 129.9 (C-5), 130.4 (C-4), 131.6
(C-3), 138.4 (C-6), 167.1 (C-1); EI MS m/z 504 (86,
[M+]), 439 (100, [M+−C5H5]); Anal. Calc. for
C27H33ClO2STi: C, 64.22; H, 6.59. Found: C, 64.35; H,
6.49.
3. Experimental
All operations were performed under an inert atmo-
sphere of argon using standard Schlenk-line or glove-
box techniques. Diethyl ether was distilled from sodium
benzophenone ketyl. Pentane and hexane were purified
by distillation over sodium–benzophenone ketyl–
triglyme. tbmpH2 [15], Ti(h5-C5H5)Cl3 [16], Ti(h5-
C5Me5)Cl3 [17] and Ti{h5-1,3-(SiMe3)2C5H3}Cl3 [18]
were synthesized according to published procedures.
LinBu (Aldrich), NaH (Aldrich), MgMeCl (Aldrich)
and Mg(CH2C6H5)Cl (Aldrich) were used as received.
Lithium [19] and Grignard [20] solutions were titrated
prior to use. NMR spectra were recorded on a Bruker
DRX 400 or on a Varian Unity 300 spectrometer (1H,
400.1 MHz, 299.9 MHz; 13C, 75.43, 100.6 MHz) in
3.2. Ti(tbmp)(p5-C5H5)Me (2)
Methylmagnesium chloride (0.23 ml of a 3 M solu-
tion in THF) was added to a precooled ethereal solu-
tion of 1 (0.33 g, 0.66 mmol) at −78°C (ca. 10 ml) and
the reaction mixture was allowed to warm slowly to r.t.
overnight. All volatiles were removed in vacuo and the
residue was extracted with pentane (ca. 30 ml) and the
extracts concentrated. Cooling the solution to −78°C
1
CDCl3 at 298 K. Chemical shifts (in ppm) for H and
13C were referenced internally using the residual solvent

F. Amor et al. / Journal of Organometallic Chemistry 621 (2001) 3–9
7
overnight precipitated 0.22 g of an orange solid (68%):
4-CH3), 7.01 (d, 4JHH=2 Hz, 2H, 5-H), 7.34 (d,
4JHH=2 Hz, 2H, 3-H); 13C{1H}-NMR
12.5
1H-NMR l 1.32 (s, 18H, 6-C(CH3)3), 1.34 (s, TiCH3),
l
4
2.29 (s, 6H, 4-CH3), 6.56 (s, 5H, C5H5), 7.06 (d, JHH
=
(C5(CH3)5), 20.7 (4-CH3), 30.0 (6-C(CH3)3), 34.7 (6-
C(CH3)3), 60.8 (TiCH3), 124.7 (C5(CH3)5), 125.3 (C-5),
127.9 (C-2), 129.7 (C-4), 131.9 (C-3), 137.7 (C-6), 165.5
(C-1); EI MS m/z 537 (100, [M+−CH3]); Anal. Calc.
for C33H46O2STi: C, 71.49; H, 8.30. Found: C, 71.74;
H, 8.47.
2 Hz, 2H, 5-H), 7.44 (d, 4JHH=2 Hz, 2H, 3-H);
13C{1H}-NMR l 20.7 (4-CH3), 29.7 (6-C(CH3)3), 35.1
(6-C(CH3)3), 58.1 (TiCH3), 115.4 (C5H5), 128.4 (C-2),
128.9 (C-4), 129.4 (C-5), 132.9 (C-3), 137.6 (C-6), 166.1
(C-1); EI MS m/z 469 (100, M+-CH3); Anal. Calc. for
C28H36O2STi: C, 69.41; H, 7.49. Found: C, 69.34; H,
7.72.
3.6. Ti(tbmp){p5-1,3-(SiMe3)2C5H3}Cl (6)
3.3. Ti(tbmp)(p5-C5H5)(CH2Ph) (3)
A solution of tbmpH2 (0.87 g, 2.44 mmol) in hexane
(ca. 25 ml) was added to a suspension of NaH (0.12 g,
4.88 mmol) in hexane (ca. 20 ml) and the mixture was
A solution of 1 (0.40 g, 0.79 mmol) in diethyl ether
(ca. 15 ml) was treated with benzylmagnesium chloride
(0.77 ml of a 1.24 M solution in THF) at −78°C. After
stirring for 16 h at r.t., all volatiles were removed in
vacuo. The residue was extracted into hexane (ca. 30
ml) and the solvent was removed. Recrystallization
from pentane at −30°C afforded dark yellow crystals
stirred for 16 h.
A
solution of Ti{h5-1,3-
(SiMe3)2C5H3}Cl3 (0.89 g, 2.44 mmol) in diethyl ether
(ca. 60 ml) was added to the mixture and stirred for 4
h. The resulting solution was filtered and concentrated
to ca. 10 ml and cooled to −20°C overnight to afford
0.91 g of a dark red solid. From the mother liquor a
second crop was obtained (0.49 g); combined yield 1.40
1
(0.30 g, 68%): H-NMR l 1.41 (s, 18H, 6-C(CH3)3),
1
2.26 (s, 6H, 4-CH3), 3.14 (s, 2H, TiCH2), 6.31 (s, 5H,
g (81%): H-NMR l 0.24 (s, 18H, Si(CH3)3), 1.27 (s,
4
C5H5), 7.06 (d, JHH=2 Hz, 2H, 5-H), 7.26, 7.28, 7.30
18H, 6-C(CH3)3), 2.24 (s, 6H, 4-CH3), 6.99 (br, 2H,
5-H) overlapping 7.01 (br, 1H, 7-H), 7.24 (br, 2H,
9,10-H) overlapping 7.25 (br, 2H, 3-H); 13C{1H}-NMR
l −0.2 (Si(CH3)3), 20.7 (4-CH3), 30.2 (6-C(CH3)3),
35.2 (6-C(CH3)3), 128.1 (C-2), 128.5 (C-5), 129.9 (C-4),
130.0 (C-9,10), 131.0 (C-7), 132.4 (C-3), 137.6 (C-8,11),
138.1 (C-6), 166.5 (C-1); EI MS m/z 648 (100, [M+]),
439 (96, [M+-(SiMe3)2C5H3]); Anal. Calc. for
C33H49ClO2SSi2Ti: C, 61.05; H, 7.61. Found: C, 61.21;
H, 7.57.
(br, 5H, C6H5), 7.40 (d, 4JHH=2 Hz, 2H, 3-H);
13C{1H}-NMR l 20.7 (4-CH3), 29.9 (6-C(CH3)3), 35.4
(6-C(CH3)3), 81.2 (TiCH2), 117.9 (C5H5), 122.6, 126.4
(C6H5), 128.0 (C-5), 128.9 (C-2), 129.2 (C-4), 129.6
(C6H5), 133.2 (C-3), 137.9 (C-6), 152.4 (ipso C6H5),
166.7 (C-1); Anal. Calc. for C34H40O2STi: C, 72.87; H,
7.14. Found: C, 72.96; H, 7.18.
3.4. Ti(tbmp)(p5-C5Me5)Cl (4)
This compound was prepared following a procedure
3.7. Ti(tbmp){p5-1,3-(SiMe3)2C5H3}Me (7)
analogous to that described to prepare
1 from
Li2(tbmp) (0.50 g, 1.35 mmol) and Ti(h5-C5Me5)Cl3
(0.37 g, 1.30 mmol) and isolated as red crystals; yield
0.58 g (79%): 1H-NMR l 1.35 (s, 18H, 6-C(CH3)3), 2.25
(s, 15H, C5(CH3)5), 2.26 (s, 6H, 4-CH3), 7.05 (d,
Following a procedure analogous to that described to
prepare 2, the chloro complex 6 (0.35 g, 0.54 mmol)
and methylmagnesium chloride (0.20 ml of a 3 M
solution in THF) were reacted to give yellow–red mi-
cro-crystals; yield 0.25 g (75%): 1H-NMR l 0.18 (s,
18H, Si(CH3)3), 1.26 (s, 18H, 6-C(CH3)3), 1.31 (s, 3H,
4
4JHH=2 Hz, 2H, 5-H), 7.23 (d, JHH=2 Hz, 2H, 3-H);
13C{1H}-NMR l 13.0 (C5(CH3)5), 20.9 (4-CH3), 31.8
(6-C(CH3)3), 34.8 (6-C(CH3)3), 126.5 (C-5), 128.0 (C-3),
129.5 (C5(CH3)5), 130.1 (C-4), 131.9 (C-2), 137.7 (C-6),
161.0 (C-1); EI MS m/z 574 (89, [M+]), 539 (41,
[M+−Cl]), 439 (100, [M+−C5Me5]); Anal. Calc. for
C32H43ClO2STi: C, 66.83; H, 7.54. Found: C, 67.05; H,
7.64.
4
TiCH3), 2.23 (s, 6H, 4-CH3), 6.68 (t, JHH=2 Hz, 1H,
7-H), 6.76 (d, 4JHH=2 Hz, 2H, 9,10-H), 6.99 (d,
4
4JHH=2 Hz, 2H, 5-H), 7.33 (d, JHH=2 Hz, 2H, 3-H);
13C{1H}-NMR l −0.1 (Si(CH3)3), 20.7 (4-CH3), 30.2
(6-C(CH3)3), 35.1 (6-C(CH3)3), 60.5 (TiCH3), 125.4 (C-
9,10), 127.6 (C-2), 128.2 (C-5), 128.5 (C-4), 129.6 (C-
8,11), 131.5 (C-7), 132.3 (C-3), 137.3 (C-6), 166.8 (C-1);
Anal. Calc. for C34H52O2SSi2Ti: C, 64.98; H, 8.28.
Found: C, 64.94; H, 8.59.
3.5. Ti(tbmp)(p5-C5Me5)Me (5)
Following a procedure analogous to that described to
prepare 2, the chloro complex 4 (0.21 g, 0.36 mmol)
was reacted with methylmagnesium chloride (0.13 ml of
a 3 M solution in THF) to give orange crystals; yield
0.15 g (75%): H-NMR l 0.86 (s, 3H, TiCH3), 1.27 (s,
18H, 6-C(CH3)3), 2.07 (s, 15H, C5(CH3)5), 2.24 (s, 6H,
3.8. Ti(tbmp){p5-1,3-(SiMe3)2C5H3}(CH2Ph) (8)
Following a procedure analogous to that described to
prepare 3, the chloro complex 6 (0.35 g, 0.54 mmol)
was reacted with benzylmagnesium chloride (0.45 ml of
1

8
F. Amor et al. / Journal of Organometallic Chemistry 621 (2001) 3–9
a 1.24 M solution in THF) to give a yellow–brown
solid; yield 0.38 g (70%): H-NMR l −0.06 (s, 18H,
methods (SHELXS-86) [21b] and difference Fourier syn-
theses and refined by full-matrix least-squares against
all F2o data (SHELXL-93) [21c] (473 parameters). The
non-hydrogen atoms of the complex were refined with
anisotropic displacement parameters and the hydrogen
atoms were refined with isotropic displacement parame-
ters. The crystal structure shows diethyl ether included
around a centre of inversion. Split positions of the
severely disordered molecule could be resolved and
refined with isotropic displacement parameters. Hydro-
gen atoms of this molecule were not included in the
structure factor calculation. The refinement converged
with R=0.0448, wR2=0.1110 for all observed Fo data,
goodness-of-fit 1.078.
1
Si(CH3)3), 1.32 (s, 18H, 6-C(CH3)3), 2.18 (s, 6H, 4-
4
CH3), 3.15 (s, 2H, TiCH2), 6.47 (d, JHH=2 Hz, 2H,
4
4
5-H), 6.96(d, JHH=2 Hz, 2H, 3-H), 7.02 (t, JHH=2
Hz, 1H, 7-H), 7.20, 7.24 (br, 2H, C6H5), 7.26 (br, 2H,
9,10-H), 7.27 (br, 2H, C6H5); 13C{1H}-NMR l −0.2
(Si(CH3)3), 20.8 (4-CH3), 30.2 (6-C(CH3)3), 35.2 (6-
C(CH3)3), 82.6 (TiCH2), 122.6 (C6H5), 125.9 (C-8,11),
126.5, 127.9 (C6H5), 128.3 (C-2), 128.5 (C-5), 128.9
(C-4), 129.2 (C-9,10), 131.0 (C-7), 133.4 (C-3), 138.1
(C-6), 153.1 (ipso C6H5), 166.0 (C-1); EI MS m/z 613
(100, [M+−C7H7]); Anal. Calc. for C40H56O2SSi2Ti: C,
68.20; H, 7.95. Found: C, 67.90; H, 7.80.
3.9. X-ray crystal structure analysis of 1
4. Supplementary material
Crystallographic data are summarized in Table 2.
Single crystals of 1 were grown from a diethyl ether/
hexane solution at −30°C. Data were collected using
an ENRAF–Nonius CAD4 diffractometer (l-scan
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC No. 154412. Copies of this infor-
mation may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge CB2
1EZ, UK (fax: +44-1223-336033; e-mail: deposit@
ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
,
mode, Mo–Ka radiation, u=0.7107 A). Data correc-
tion for Lorentz polarization and absorption (using
C-scans) was carried out using the program system
MOLEN [21a]. From 7400 measured reflections, 6993
were independent. The structure was solved using direct
Table 2
Acknowledgements
Crystallographic data for Ti(tbmp)(h5-C5H5)Cl (1)
We gratefully acknowledge the financial support by
the Fonds der Chemischen Industrie.
Empirical formula
fw
C27H33ClO2STi·0.5C4H10
542.00
O
Crystal colour
Crystal size (mm)
Crystal system
Space group
Red
0.51×0.51×0.83
Triclinic
References
(
P1 (no. 2)
,
a (A)
9.715(3)
,
b (A)
12.834(3)
12.951(4)
67.95(2)
83.73(2)
76.20(2)
1453.1(7)
2
1.239
0.483
574
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3
,
V (A )
Z
Dcalc (mg m−3
)
Absorption coefficient (mm−1
F(000)
)
Temperature (K)
q range (°)
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296(2)
3 to 28
05h512; −165k516;
−175l517
7400
6993 (Rint=0.0197)
5280
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[I]2|(I)]
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0.0670, 0.1330
1.078
0.348 and −0.273
−3
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