Synthesis, hydrosilylation reactivity and catalytic properties of group 4 ansa-metallocene complexes

Polyhedron 24 (2005) 1298–1313

www.elsevier.com/locate/poly

Synthesis, hydrosilylation reactivity and catalytic properties of

group 4 ansa-metallocene complexes

a

a,

a

Santiago Gomez-Ruiz , Sanjiv Prashar ^*, Mariano Fajardo ,

´

b

b,

c

d

Antonio Antin˜olo , Antonio Otero ^*, Miguel A. Maestro , Victoria Volkis ,

d

Moris S. Eisen , Cesar J. Pastor

e

´

a

´ ´ ´

Departamento de Tecnologıa Quımica y Ambiental, ESCET, Universidad Rey Juan Carlos, 28933 Mostoles, Madrid, Spain

´ ´ ´ ´ ´

Departamento de Quımica Inorganica, Organica y Bioquımica, Universidad de Castilla-La Mancha, Facultad de Quımicas,

b

Campus Universitario, 13071-Ciudad Real, Spain

Departamento de Quı´mica Fundamental, Facultade de Ciencias, Campus da Zapateira, Universidade da Corun˜a, 15071 A Corun˜a, Spain

c

d

Department of Chemistry and Institute of Catalysis Science and Technology, Technion-Israel Institute of Technology, Haifa 32000, Israel

e

´ ´

Servicio Interdepartamental de Investigacion, Universidad Autonoma de Madrid, Cantoblanco 28049 Madrid, Spain

Received 25 January 2005; accepted 7 March 2005

Available online 23 May 2005

Abstract

The following ansa-ligand precursors, Et(H)Si(C₅H₅)₂(1), Et(H)Si(C₅HMe₄)Cl (2), Et(H)Si(C₅HMe₄)(C₅H₅) (3), Ph(H)Si(C₅H-

Me₄)Cl (4), Ph(H)Si(C₅HMe₄)(C₅H₅) (5), Ph(H)Si(C₅HMe₄)₂(6), CH₂@CHCH₂(H)Si(C₅HMe₄)Cl (7), CH₂@CHCH₂(H)Si(C₅H-

Me₄)(C₅H₅) (8), CH₂@CHCH₂(H)Si(C₅HMe₄)₂(9), and their lithium derivatives, Li₂{Et(H)Si(C₅H₄)₂} (10), Li₂{Et(H)-

Si(C₅Me₄)(C₅H₄)} (11), Li₂{Ph(H)Si(C₅Me₄)(C₅H₄)} (12), Li₂{Ph(H)Si(C₅Me₄)₂} (13), Li₂{CH₂@CHCH₂(H)Si(C₅Me₄)(C₅H₄)}

(14) and Li₂{CH₂@CHCH₂(H)Si(C₅Me₄)₂} (15) have been prepared. The group 4 metal complexes, [M{Et(H)Si(g⁵-C₅H₄)₂}Cl₂]

(M = Ti (16a), Zr (16b), Hf (16c)), [M{Et(H)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (M = Ti (17a), Zr (17b), Hf (17c)), [M{Ph(H)Si(g⁵-

C₅Me₄)(g⁵-C₅H₄)}Cl₂] (M = Ti (18a), Zr (18b), Hf (18c)), [M{Ph(H)Si(g⁵-C₅Me₄)₂}Cl₂] (M = Ti (19a), Zr (19b), Hf (19c)),

M{CH₂@CHCH₂(H)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (M = Ti (20a), Zr (20b)) and [M{CH₂@CHCH₂(H)Si(g⁵-C₅Me₄)₂}Cl₂] (M = Ti

(21a), Zr (21b), Hf (21c)) were synthesized from the reaction of the lithium ansa-derivatives and the tetrachloride salts of the tran-

sition metal. The reactivity of the group 4 metal complexes in hydrosilylation processes has been studied. The reaction of 16b, 17a

and 17b with tetravinylsilane gave [Zr{(CH₂@CH)₃SiCH₂CH₂(Et)Si(g⁵-C₅H₄)₂}Cl₂] (22b) and [M{(CH₂@CH)₃SiCH₂CH₂(Et)-

Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (M = Ti (23a), Zr (23b)), respectively. The reaction of 17a and 17b with dimethyldivinylsilane yielded

the hydrosilylation products [M{(CH₂@CH)Me₂SiCH₂CH₂(Et)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (M = Ti (24a), Zr (24b)), respectively.

23b and 24b reacted with the silane reagent HSiEt₃to form, via hydrosilylation, [Zr{(Et₃SiCH₂CH₂)₃SiCH₂CH₂(Et)Si(g⁵-

C₅Me₄)(g⁵-C₅H₄)}Cl₂] (25b) and [Zr{(Et₃SiCH₂CH₂)Me₂SiCH₂CH₂(Et)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (26b), respectively.

The previously synthesized compounds, [M{CH₂@CH(Me)Si(g⁵-C₅Me₄)₂}Cl₂] (M = Ti (27a), Zr (27b)) and [Zr{CH₂@

CHCH₂(Me)Si(g⁵-C₅Me₄)₂}Cl₂] (28b), have also been tested in reactions of hydrosilylation with SiHMeCl₂to give [M{Cl₂MeSi-

CH₂CH₂(Me)Si(g⁵- C₅Me₄)₂}Cl₂] (M = Ti (29a), Zr (29b)) and [Zr{Cl₂MeSiCH₂CH₂CH₂(Me)Si(g⁵-C₅Me₄)₂}Cl₂] (30b). All the

zirconocene compounds are active to varying degrees as catalysts in the polymerization of ethylene. The molecular structures of

21b and 21c have been determined by single crystal X-ray diﬀraction studies.

Keywords: ansa-Metallocene complexes; Titanium; Zirconium; Hafnium; Hydrosilylation; Polymerization

*

Corresponding author. Tel.: +34 914887186; fax: +34 914888143.

E-mail address: sanjiv.prashar@urjc.es (S. Prashar).

doi:10.1016/j.poly.2005.03.056

´

S. Gomez-Ruiz et al. / Polyhedron 24 (2005) 1298–1313

1299

1. Introduction

2. Results and discussion

The catalytic activity of group 4 metallocene com-

plexes in the polymerization of oleﬁns has been the

principal reason for the dramatic growth in interest to-

wards these compounds [1]. The main focus of this re-

search ﬁeld is centred on the design of metallocene

complexes towards the goal of ‘‘made to measure’’

catalysts that can direct the catalytic reaction in pro-

ducing polymers with desired physical properties.

ansa-Cyclopentadienyl systems are now widely recog-

nized to aﬀord better catalytic activity and selectivity

in the polymerization of oleﬁns than their non-ansa

counterparts [2]. Recent studies have demonstrated

that the incorporation of the ansa-bridge may have a

profound inﬂuence on the chemical behaviour of these

complexes [3].

Industry requirements for the development of sup-

ported metallocene polymerization catalysts, that can

oﬀer homogeneous single-site selectivity in a heteroge-

neous medium, is presently of utmost importance.

Several studies on immobilized catalysts have recently

been published [4]. The immobilization of the catalyst

is normally achieved by the introduction of functional

groups in the ligand system and their interaction

with the surface of an inorganic oxide with the

metallocene framework remaining, in most cases,

unaltered [5].

Suzuki et al. [5d] have reported the hydrosilylation

of ansa-zirconocene complexes with vinyl substituents

at the silicon ansa bridge to give derivatives which

were subsequently supported on silica. In a similar

manner OÕHare and co-worker [5e] have reported

the immobilization on silica of an ansa-bisindenyl

complex. Alt et al. [6] have also recently published

their work relating to the modiﬁcation by hydrosilyla-

tion of ansa-cyclopentadienyl ligands and their subse-

quent incorporation in group 4 metallocene systems.

Collins and co-workers [5a] have reported the anchor-

ing, on modiﬁed silica surfaces, of ansa-metallocene

complexes via hydrosilylation reactions. Seyferth and

Wyrwa [7] have also carried out work incorporating

The ligand systems, Et(H)Si(C₅H₅)₂(1), Et(H)-

Si(C₅HMe₄)Cl (2), Et(H)Si(C₅HMe₄)(C₅H₅) (3), Ph(H)-

Si(C₅HMe₄)Cl (4), Ph(H)Si(C₅HMe₄)(C₅H₅) (5), Ph(H)

Si(C₅HMe₄)₂(6), CH₂@CHCH₂(H)Si(C₅HMe₄)-Cl (7),

CH₂@CHCH₂(H)Si(C₅HMe₄)(C₅H₅) (8) and CH₂@CH-

CH₂(H)Si(C₅HMe₄)₂(9) were prepared as yellow oils fol-

lowing previously reported synthetic protocols (Schemes

1 and 2) and isolated as mixtures of the double bond po-

sition isomers [8,9]. In the preparation of 2 and 4, an ex-

cess of the dichlorosilane reagent was used in order to

1

favour monosubstitution. 1–9 were characterized by H

NMR spectroscopy and electron impact mass spectrom-

etry (see Section 5). The ansa-biscyclopentadiene com-

pounds, 1, 3, 5, 6, 8 and 9 were lithiated in the

traditional manner with n-butyllithium, to give the dili-

thium derivates, Li₂{Et(H)Si(C₅H₄)₂} (10), Li₂{Et(H)-

Si(C₅Me₄)(C₅H₄)} (11), Li₂{Ph(H)Si(C₅Me₄)-(C₅H₄)}

(12), Li₂{Ph(H)Si(C₅Me₄)₂} (13), Li₂{CH₂@ CHCH₂-

(H)Si(C₅Me₄)(C₅H₄)} (14) and Li₂{CH₂@CH-CH₂(H)-

Si(C₅Me₄)₂} (15), in high yields.

The reaction of 10–15 with either [TiCl₄(THF)₂],

ZrCl₄or HfCl₄, yielded the corresponding ansa-metallo-

cene (IV) dichloride complexes, [M{Et(H)Si(g⁵-C₅H₄)₂}-

Cl₂] (M = Ti (16a), Zr (16b), Hf (16c)), [M{Et(H)Si(g⁵-

C₅Me₄)(g⁵-C₅H₄)}Cl₂] (M = Ti (17a), Zr (17b), Hf

(17c)), [M{Ph(H)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (M = Ti

(18a), Zr (18b), Hf (18c)), [M{Ph(H)Si(g⁵-C₅Me₄)₂}Cl₂]

(M = Ti (19a), Zr (19b), Hf (19c)), [M{CH₂@

CHCH₂(H)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (M = Ti (20a),

Zr (20b)) and [M{CH₂@ CHCH₂(H)Si(g⁵-C₅Me₄)₂}Cl₂]

(M = Ti (21a), Zr (21b), Hf (21c)) (Scheme 3).

H

Et

H

Et

2LiBuⁿ

Si

Li₂

1

10

½HSiEtCl₂

group

dendrimers.

4

metallocene fragments in organosilicon

As part of our ongoing studies in ansa-metallocene

complexes [8], we recently published our initial results

on the modiﬁcation of the ansa-ligand framework via

hydrosilylation reactions [9]. As a continuation of this

work we now report the synthesis of new group 4

ansa-metallocene complexes and the reactivity of the

ansa-bridge Si–H bond in the hydrosilylation of unsat-

urated silane substrates. We also describe the hydrosi-

lylation of vinyl or allyl substituents at the silicon

ansa bridge of group 4 metallocene complexes. The

catalytic activity of the ansa-zirconocene complexes

in the polymerization of ethylene is included.

Na

Li

½HSiRCl₂

R

H

R

2LiBuⁿ

Si

Li₂

R = Ph (6);

R = CH₂CH=CH₂(9)

R = Ph (13);

R = CH₂CH=CH₂(15)

Scheme 1.

´

S. Gomez-Ruiz et al. / Polyhedron 24 (2005) 1298–1313

1300

R

Et

Cl

Si

M

H

Si Cl

H

HSiRCl₂

M = Ti (16a); Zr (16b); Hf (16c)

Li

R = Et (2);

R = Ph (4);

H

Et

R = CH₂CH=CH₂(7)

Si

Li₂

MCl₄

H

R

Na(C₅H₅)

Si

Li₂

H

R

H

R

2LiBuⁿ

Si

Li₂

Si

Li₂

R

H

Cl

Si

M

R = Et (11);

R = Ph (12);

R = CH₂CH=CH₂(14)

R = Et (3);

R = Ph (5);

R = CH₂CH=CH₂(8)

R = Et (17), Ti a; Zr b; Hf c;

R = Ph (18), Ti a; Zr b; Hf c;

R = CH₂CH=CH₂(20), Ti a; Zr b

Scheme 2.

R

Cl

Si

M

16–21 were isolated as crystalline solids and charac-

1

H

terized spectroscopically.¹The H NMR spectra for 16

showed the expected signals, namely 4 multiplets in

the region d 6.0–7.2, corresponding to the C₅ring pro-

tons, and two multiplets, at ca. d 1.1 and 1.4, assigned

to the ethyl group. A triplet, at ca. d 5.1, was observed

for the proton bonded directly to the silicon atom.

The mixed cyclopentadienyl chiral complexes 17, 18

and 20 gave eight signals assigned to the four protons

of the unsubstituted cyclopentadienyl moiety and to

the four methyl groups of the tetramethylcyclopentadie-

nyl fragment. For 17 the a-protons of the ethyl unit are

diastereoscopic and give rise to two overlapping multi-

plet signals (d 1.4) with a further multiplet being ob-

served for the b-protons (d 1.5). The Si–H proton

resonates (d 5.2) as a pseudo-triplet due to its coupling

with the two inequivalent a-protons of the ethyl group.

For 18 three multiplets for the phenyl moiety (d 7.3, 7.6

and 8.0) and a singlet (d 5.9) assigned to the Si–H proton

were observed. For 20 the a-protons of the allyl unit are

again diastereoscopic and were observed as an unre-

solved multiplet (d 2.5) arising from both geminal and

vicinal couplings. Further multiplets were observed for

the central CH (d 6.1) and terminal oleﬁnic protons (d

5.2 and 5.3, cis and trans, respectively, with respect to

H_b). As in the case of 17, the Si–H signal in 20 was ob-

served as a pseudo-triplet (d 5.2). The C_ssymmetric

R = Ph (19), Ti a; Zr b; Hf c;

R = CH₂CH=CH₂(21), Ti a; Zr b; Hf c

Scheme 3.

glet for the Si–H proton (d 6.0) were also observed. For

21, the ¹H NMR spectra were completed with the

assignment of four multiplets (d 2.6, 5.2, 5.3 and 6.1)

and a triplet (d 5.3) to the allyl and Si–H protons,

respectively. The ¹³C{¹H} NMR spectra for 16–21

showed the expected signals for the diﬀerent ligand sys-

tems present (see Section 5). Signals for the allyl carbons

of 20 and 21 were observed in the ¹³C NMR spectra at

ca. d 20, 132 and 117 corresponding to the silicon

bonded, central and terminal carbons, respectively.

The signal due to the ansa-bridge silicon atom in 16–

21 was observed in the ²⁹Si NMR spectra with the nat-

ure of this signal depending on the substituents present;

16, 17, 20 and 21 a doublet of multiplets and 18 and 19 a

doublet. The multiplicity of the signal corresponds to

the coupling of the silicon atom with its hydride substi-

tuent and the a-protons of the ethyl or allyl group.

The molecular structures of 21b and 21c were estab-

lished by single crystal X-ray diﬀraction studies. The

molecular structures and atomic numbering schemes

are shown in Figs. 1 and 2. Selected bond lengths and

angles for 21b and 21c are given in Table 1. In the case

of 21c, there are two distinct molecules in the asymmet-

ric unit. A disordered toluene molecule was also located

in the asymmetric unit.

1

complexes 19 and 21 gave in the H NMR spectra, four

singlets, in the region d 1.6–2.2, corresponding to the

per-methyl substituted ansa-ligand. For 19, three multi-

plets for the phenyl moiety (d 7.3, 7.5 and 8.0) and a sin-

For 21b and 21c, the usual bent metallocene confor-

mation is observed with the geometry around the metal

atom being pseudo-tetrahedral. The ansa ligand chelates

1

We were unable to obtain the hafnium derivative of 20 with

suﬃcient purity.

´

S. Gomez-Ruiz et al. / Polyhedron 24 (2005) 1298–1313

1301

Table 1

˚

Selected bond lengths (A) and angles (ꢁ) for 21b and 21c

21b

21c

M–Cent(1)

2.229

2.217

2.219

2.206

2.202

2.209

M–Cent(2)

av M–C(Cent(1))^a

av M–C(Cent(2))^a

M–Cl(1)

2.531

2.522

2.517

2.513

2.516

2.425(3)

2.413(3)

1.864(8)

1.597

2.402(2)

2.412(2)

1.835(8)

2.413(2)

2.416(2)

1.879(8)

M–Cl(2)

Si(1)–C(19)

Si(1)–H(1)

C(19)–C(20)

C(20)–C(21)

1.51(1)

1.33(1)

1.53(1)

1.26(1)

Cent(1)–M–Cent(2)

Si(1)–C(1)–Cent(1)

Si(1)–C(10)–Cent(2)

C(1)–Si(1)–C(10)

Cl(1)–M–Cent(1)

Cl(1)–M–Cent(2)

Cl(2)–M–Cent(1)

Cl(2)–M–Cent(2)

Cl(1)–M–Cl(2)

128.5

160.7

162.7

96.5(2)

106.5

106.3

106.7

107.0

97.54(8)

106.6

106.3

112.0

129.05

161.37

161.19

96.2(3)

105.70

106.50

106.22

106.23

99.33(6)

128.65

160.87

161.27

95.9(3)

105.99

106.02

106.58

107.78

97.51(6)

Fig. 1. Molecular structure and atom-labelling scheme for

[Zr{CH₂@CHCH₂(H)Si(g⁵-C₅Me₄)₂}Cl₂] (21b) with thermal ellipsoids

at 30% probability.

H(1)–Si(1)–C(1)

H(1)–Si(1)–C(11)

H(1)–Si(1)–C(21)

Si(1)–C(19)–C(20)

C(19)–C(20)–C(21)

108.7(5)

124.8(9)

109.4(5)

126.3(9)

Cent(1) and Cent(2) are the centroids of C(1)–C(5) and C(10)–C(14),

respectively.

a

Refers to the average bond distance between Zr or Hf and the

carbon atoms of the C₅ring of the corresponding cyclopentadienyl

moiety.

are typical for carbon carbon single (C(19)–C(20)) and

double bonds (C(20)–C(21)), respectively. The angles

Si(1)–C(19)–C(20) 108.7(5)ꢁ and 109.4(5)ꢁ and C(19)–

C(20)–C(21) 124.8(9)ꢁ and 126.3(9)ꢁ indicate that

C(19) and C(20) are sp³and sp²hybridized, respectively.

Selected structural data of 21b and 21c can be compared

with similar ansa-metallocene complexes using Table 2.

We have previously reported the modiﬁcation of

ansa-metallocene systems via hydrosilylation processes

[9] and in order to gain a better understanding into the

possible electronic or steric factors that may inﬂuence

the outcome of these reactions we have tested 16–21 as

hydrosilylation reagents. The hydrosilylation of Si(CH@

CH₂)₄by 16–21 in the presence of the Karstedt catalyst

(divinyltetramethylsiloxane Pt(0)) was attempted. The

per-methyl substituted ansa-complexes 19 and 21 did

not react, inferring that the Si–H bond is not suﬃciently

reactive (even at high temperatures) to participate in the

hydrosilylation reaction. This may be due to electronic

eﬀects caused by the electrodonating nature of the

methyl ring substituents which translates to a less reac-

tive Si–H bond [13]. The mixed cyclopentadienyl com-

plexes (with four fewer methyl substituents) 17, 18 and

20 did react with Si(CH@CH₂)₄giving the product

formed by the reaction of only one of the double bonds

of the silane substrate. Only in the case of 17a and 17b

were we able to isolate the ﬁnal product with high purity

Fig. 2. Molecular structure and atom-labelling scheme for

[Hf{CH₂@CHCH₂(H)Si(g⁵-C₅Me₄)₂}Cl₂] (21c) with thermal ellipsoids

at 50% probability.

the zirconium or hafnium atom and both C₅rings are

bound to the metal in an g⁵mode. The centroids of

the tetramethylcyclopentadienyl rings form an angle

with the metal atom of 128.5ꢁ 21b and 129.05ꢁ and

128.65ꢁ 21c, which is typical for dichloride group 4

ansa-metallocene complexes. In 21b the hydrogen atom

(H(1)) bonded to the silicon atom was located in the dif-

ference map. The carbon atoms of the allyl moiety in

21b are disordered, therefore we make no reference to

the bond distances and angles of this fragment. How-

ever, in 21c the allyl carbon atoms were clearly resolved

and exhibit bond distances of C(19)–C(20) 1.51(1) and

˚

1.53(1) A and C(20)–C(21) 1.33(1) and 1.26(1) A which

´

S. Gomez-Ruiz et al. / Polyhedron 24 (2005) 1298–1313

1302

Table 2

Selected structural data of some ansa-zirconocene and hafnocene complexes

a

˚

M–Cp (A)

˚

M–Cl (A)

Complex

Cp–M–Cp (ꢁ)

Cl–M–Cl (ꢁ)

C_(cp)–Si–C_(cp)(ꢁ)

Reference

[Zr{CH₂@CHCH₂(H)Si(g⁵-C₅Me₄)₂}Cl₂] (21b)

[Zr{Me(H)Si(g⁵-C₅Me₄)₂}Cl₂]

2.223

2.230

2.329

2.220

2.235

2.213

2.206

2.223

2.224

2.217

2.419

2.427

128.5

128.6

128.76

128.7

129.05

128.65

129.2

97.54(8)

98.85(6)

92.28

96.5(2)

96.15(19)

95.7(1)

95.8(2)

96.3(1)

96.2(3)

95.9(3)

95.1(3)

95.3(2)

96.5(2)

this work

[9]

[10]

[Zr{Me₂Si(g⁵-C₅Me₄)₂}Cl₂]

2.4334(7)

2.418

[Zr{Me(CH₂@CH)Si(g⁵-C₅Me₄)₂}Cl₂]

[Zr{(CH₂@CH)₂Si(g⁵-C₅Me₄)₂}Cl₂]

[Hf{CH₂@CHCH₂(H)Si(g⁵-C₅Me₄)₂}Cl₂] (21c)

99.32(7)

99.24(3)

99.33(6)

97.51(6)

98.0(1)

[8e]

[11]

2.4333

2.407

2.415

this work

[Hf{Me₂Si(g⁵-C₅Me₄)₂}Cl₂]

[Hf{Et₂Si(g⁵-C₅Me₄)₂}Cl₂]

2.407(2)

2.407

2.405

[12]

98.75(8)

97.98(7)

[Hf{(CH₂@CH)₂Si(g⁵-C₅Me₄)₂}Cl₂]

129.2

˚

C–C (A)

˚

C@C (A)

Si–C–C (ꢁ)

CAC@C (ꢁ)

Reference

[Zr{Me(CH₂@CHCH₂)Si(g⁵-C₅H₄)₂}Cl₂]

1.49(3)

1.49(1)

1.51(1)

1.53(1)

1.26(5)

1.32(1)

1.33(1)

1.26(1)

111.6(8)

113.8(7)

108.7(5)

109.4(5)

124(5)

123(1)

[8e]

[Zr{Me(CH₂@CHCH₂)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂]

[Hf{CH₂@CHCH₂(H)Si(g⁵-C₅Me₄)₂}Cl₂] (21c)

124.8(9)

126.3(9)

this work

a

Cp refers to the C₅Me₄moiety.

and although the experimental conditions were directed

towards the polyhydrosilylation of the silane substrate

only the monohydrosilylation derivative, [M{(CH₂@

CH)₃SiCH₂CH₂(Et)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (M =

Ti (23a), Zr (23b)), was obtained (Scheme 4). This fact

may be due to steric hindrance in the hypothetical tet-

ra-substitution of the silane substrate by four metallo-

cene units. However, Alt et al. [6a] have recently

prepared tetranuclear complexes via the hydrosilylation

of ansa-cyclopentadienyl ligands and their subsequent

incorporation in group 4 ansa-metallocene systems.

Our synthetic strategy diﬀers from that used by Alt in

that in our case the reactivity takes place at the group

4 ansa-metallocene complex and not from previous

modiﬁcation of the organic ligand.

the cyclopentadienyl moieties namely four singlets and

four multiplets. The three unreacted vinyl groups of

the silane gave an ABX system in the H NMR spectra

1

and signals at ca. d 133 (C_a) and 136 (C_b) in the ¹³C{¹H}

NMR spectra. The –CH₂CH₂– fragment, resulting from

the hydrosilylation of the vinyl group, gave a complex

set of multiplets with geminal and vicinal couplings in

the ¹H NMR spectra. Two signals were observed in

the ²⁹Si{¹H} NMR spectra at ca. d ꢀ18 and ꢀ9, corre-

sponding to the vinyl substituted and ansa bridge silicon

atoms, respectively. The hydrosilylation reaction can

also give the alternative regioisomer, [M{(CH₂@

CH)₃Si(CH₃)CH(Et)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂], via

a-addition [14]. This minor product was detected, in

1

quantities of ca. 5–10%, by H NMR spectroscopy.

23a and 23b were isolated as red and yellow oils,

respectively, and characterized by NMR spectroscopy.

The ansa-metallocene complex without ring substitu-

ents 16b was also tested in this reaction. It was hoped

that the complete absence of electrodonating ring sub-

stituents would aid in the polyhydrosilylation of the

tetravinylsilane. However, only the monohydrosilylation

product, [Zr{(CH₂@CH)₃SiCH₂CH₂(Et)Si(g⁵-C₅H₄)₂}-

Cl₂] (22b), was detected (Scheme 5). Nevertheless the

Si–H bond in 16b was shown to be more reactive than

its methyl substituted counterparts 17–21 with the reac-

tion of hydrosilylation being complete after 3 h at room

temperature whereas for 23a and 23b the experimental

conditions required were 100 ꢁC and 40 h reaction time.

22b was isolated as a yellow oil and characterized by

NMR spectroscopy giving data similar to 23a and 23b

(see Section 5).

1

The H NMR spectra showed the expected signals for

Et

Cl

Si

M

H

M = Ti (17a); Zr (17b)

Si

Et

Karstedt Catalyst

Cl

Similar reactions have been carried out between 17a

and 17b and dimethyldivinylsilane and gave the

products [M{(CH₂@CH)Me₂SiCH₂CH₂(Et)Si(g⁵-C₅Me₄)

(g⁵-C₅H₄)}Cl₂] (M = Ti (24a), Zr (24b)), as red and

yellow oils, respectively, formed by the hydrosilylation

of only one of the double bonds of the silane substrate

Si

M

Si

M = Ti (23a); Zr (23b)

Scheme 4.

´

S. Gomez-Ruiz et al. / Polyhedron 24 (2005) 1298–1313

1303

Et

H

Et

Cl

Si

Zr

Si

Zr

Si

16b

Karstedt Catalyst

23b

Si

Et

3HSiEt₃

Karstedt Catalyst

Cl

Si

Zr

Si

Et

Cl

Si

Zr

22b

Si

Scheme 5.

25b

Scheme 7.

(Scheme 6). The NMR spectra of 24a and 24b are simi-

lar in all aspects to those previously discussed for 22 and

23 and showed in addition the presence of the minor reg-

ioisomer produced by a-addition (5–10%).

NMR spectra showed the expected signals for the

C₅H₄and C₅Me₄moieties. In addition two multiplets,

assigned to the ethyl groups of SiEt₃, and a complex

set of multiplets, corresponding to the two distinct

–CH₂CH₂– fragments, were observed. The presence of

the minor a-addition regioisomers was again detected

(5–10%). ²⁹Si{¹H} NMR spectra revealed three signals

corresponding to the three distinct silicon atoms present.

The hydrosilylation of the previously reported com-

plexes [M{CH₂@CH(Me)Si(g⁵-C₅Me₄)₂}Cl₂] (M = Ti

(27a), Zr (27b)) and [Zr{CH₂@CHCH₂(Me)Si(g⁵-

C₅Me₄)₂}Cl₂] (28b) [8e], by HSiMeCl₂has successfully

been carried out. The reaction, in the presence of the

Karstedt catalyst, gave after two hours reaction time

the b-hydrosilylation products [M{Cl₂MeSiCH₂CH₂-

(Me)Si(g⁵-C₅Me₄)₂}Cl₂] (M = Ti (29a), Zr (29b)) and

[Zr{Cl₂MeSiCH₂CH₂CH₂(Me)Si(g⁵-C₅Me₄)₂}Cl₂] (30b)

Further hydrosilylation of the vinyl groups of 22–24

was not possible when the hydrogen–silicon bond corre-

sponded to the ansa-metallocene complexes. It appears

that the reaction of one of the vinyl groups with the

ansa-metallocene complex deactivates the remaining vi-

nyl groups towards hydrosilylation by the Si–H of the

ansa bridge. This may be attributed to electronic and/

or steric eﬀects. However, with triethylsilane, hydrosily-

lation took place at all the remaining vinyl groups of 23b

and 24b, to give [Zr{(Et₃SiCH₂CH₂)₃SiCH₂CH₂(Et)Si-

(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (25b) and [Zr{(Et₃SiCH₂-

CH₂)Me₂SiCH₂CH₂(Et)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (26b)

(Schemes 7 and 8).

25b and 26b were isolated as yellow oils and charac-

terized by NMR spectroscopy. The reaction was deemed

to have gone to completion by the absence of any signals

1

in H and ¹³C{¹H} NMR spectroscopy corresponding

1

to the vinyl groups of the parent complexes. The H

Et

Cl

Si

Zr

Et

Cl

Si

M

Si

H

24b

M = Ti (17a); Zr (17b)

HSiEt₃

Et

Karstedt Catalyst

Si

Et

Karstedt Catalyst

Cl

Si

Zr

Cl

Si

M

Si

M = Ti (24a); Zr (24b)

26b

Scheme 8.

Scheme 6.

´

S. Gomez-Ruiz et al. / Polyhedron 24 (2005) 1298–1313

1304

the presence of signals due to the vinyl or allyl protons

of the starting products, 27 and 28, was not observed.

In the region of d 0.5–1.8 multiplet signals were ob-

served, two in the case of 29 (–SiCH₂CH₂Si–) and three

for 30 (–SiCH₂CH₂CH₂Si–). For 29 and 30 a singlet at d

0.4 was observed corresponding to the methyl protons

of the dichloromethylsilyl fragment. Two signals were

recorded in the ²⁹Si{¹H} NMR for 29 and 30 at ca. d

ꢀ10 and 32 and assigned to the ansa bridge and chloride

bonded silicon atoms, respectively. In the ²⁹Si{¹H}

NMR spectra of the vinyl and allyl substituted ansa-

metallocene precursors of 29 and 30 a unique signal

was observed for the ansa bridge silicon atom at

d ꢀ21.2, ꢀ22.7 and ꢀ15.6 for 27a, 27b and 28b,

respectively [15].

Cl

Si

M

M = Ti (27a); Zr (27b)

Karstedt Catalyst

HSiMeCl₂

Si

Cl

M

Si

Cl

M = Ti(29a); Zr (29b)

Scheme 9.

3. Polymerization studies

Cl

Zr

Si

Cl

The polymerization of ethylene using the zirconium

derivatives described in this paper as catalysts has

been carried out. The polymerization experiments were

conducted with a MAO–metal catalyst ratio of 3000:1,

at 20 ꢁC and at oleﬁn pressure of 2 bar for 15 min.

Polymerization was also carried out with the reference

compound [Zr(g⁵-C₅H₅)₂Cl₂], under the same experi-

mental conditions. The catalytic activities and polymer

molecular weight and distribution values are given in

Table 3.

28b

Karstedt Catalyst

HSiMeCl₂

Cl

Si

Zr

Si

Cl

30b

Scheme 10.

Complex 29b proved to be the most active catalyst

of the series. A slightly lower value was recorded for

the reference complex [Zr(g⁵-C₅H₅)₂Cl₂]. The low cat-

alytic activities observed for 22, 23b and 25 may be

due to steric factors as proposed previously by De

(Schemes 9 and 10). The presence of the minor a-addi-

tion regioisomer was also detected (5–10%).

29 and 30 were isolated as yellow solids and charac-

1

terized by NMR spectroscopy. In the H NMR spectra

Jesu

´s and co-workers [16] for similar modiﬁed metal-

Table 3

Ethylene polymerization results for 16–30 and [Zr(g⁵-C₅H₅)₂Cl₂]^a

Catalyst

Activity^b

M_w

M_w/M_g

[Zr(g⁵-C₅H₅)₂Cl₂]

23750

11100

8760

1014670

210200

186200

185240

133500

194650

156800

139460

420000

141300

717000

669000

236000

136790

483000

558000

2.1

3.2

3.1

3.3

4.1

3.4

4.0

3.1

4.7

3.1

5.4

3.0

4.8

4.6

[Zr{Et(H)Si(g⁵-C₅H₄)₂}Cl₂] (16b)

[Zr{Et(H)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (17b)

[Zr{Ph(H)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (18b)

[Zr{(CH₂@CHCH₂)(H)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (20b)

[Zr{Ph(H)Si(g⁵-C₅Me₄)₂}Cl₂] (19b)

7053

3120

15967

6373

3307

[Zr{(CH₂@CHCH₂)(H)Si(g⁵-C₅Me₄)₂}Cl₂] (21b)

[Zr{(CH₂@CH)₃SiCH₂CH₂(Et)Si(g⁵-C₅H₄)₂}Cl₂] (22b)

[Zr{(CH₂@CH)₃SiCH₂CH₂(Et)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (23b)

[Zr{(CH₂@CH)Me₂Si(CH₂CH₂)(Et)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (24b)

[Zr{(Et₃SiCH₂CH₂)₃SiCH₂CH₂(Et)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (25b)

[Zr{(Et₃SiCH₂CH₂)Me₂SiCH₂CH₂(Et)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (26b)

[Zr{CH₂@CH(Me)Si(g⁵-C₅Me₄)₂}Cl₂] (27b)

[Zr{CH₂@CHCH₂(Me)Si(g⁵-C₅Me₄)₂}Cl₂] (28b)

[Zr{Cl₂MeSiCH₂CH₂(Me)Si(g⁵-C₅Me₄)₂}Cl₂] (29b)

[Zr{Cl₂MeSiCH₂CH₂CH₂(Me)Si(g⁵-C₅Me₄)₂}Cl₂] (30b)

a

5513

7213

3367

10147

15510

16472

26898

17707

At 20 ꢁC, 2 bar monomer pressure, 200 mL toluene, [Al] = 9 · 10^ꢀ2mol L^ꢀ1, [Zr] = 3 · 10^ꢀ5mol L^ꢀ1, t_Pol= 15 min.

b

In kg Pol (mol Zr h)^ꢀ1

.

´

S. Gomez-Ruiz et al. / Polyhedron 24 (2005) 1298–1313

1305

locene systems. In general, but not always, the com-

plexes that contain a carbon carbon double bond sub-

stituent give low catalytic activities. This is most

probably due to the fact that during the polymeriza-

tion of ethylene, the vinyl or allyl groups of the

ansa-ligand co-polymerize with the monomer thus

immobilizing the metallocene complex on the polymer

chain to give a pseudo-heterogeneous catalyst. This

phenomenon with similar ansa-metallocene complexes

has previously been reported [17].

was ﬁltered and solvent removed from the ﬁltrate un-

der reduced pressure to yield the title compound as a

dark orange oil (4.54 g, 85%). ¹H NMR (400 MHz,

CDCl₃) (for the predominant isomer): d ꢀ0.38 (2H),

0.96 (3H) (m, SiEt), 3.07 (m, 2H, HC₅), 3.47 (m,

1H, SiH), 5.52 (2H), 6.00 (2H), 6.64 (2H), 6.97 (2H)

(m, C₅H₄). MS electron impact (m/e (relative inten-

sity)): 188 (25) [M⁺], 159 (19) [M⁺ꢀ Et], 123 (62)

[M⁺ꢀ C₅H₅], 93 (100) [M⁺ꢀ C₅H₅, ꢀEt].

The preparation of 2–9 was carried out in an identical

manner to 1.

4. Conclusions

5.2. Et(H)Si(C₅HMe₄)Cl (2)

In this paper we have reported the synthesis and cat-

alytic activity of new ansa-metallocene complexes con-

taining a Si–H bond which can be exploited in

reactions of hydrosilylation to modify the ligand frame-

work. The potential of translating this reactivity to the

immobilization of ansa-metallocene catalysts on distinct

substrates should be of great interest.

From Et(H)SiCl₂(5.02 g, 39.00 mmol) and

Li(C₅HMe₄) (2.50 g, 19.50 mmol). Yield: 3.57 g, 94%.

¹H NMR (400 MHz, CDCl₃) (for the predominant iso-

mer): d ꢀ0.54 (2H), 0.94 (3H) (m, SiEt), 1.85 (6H),

1.99 (3H), 2.04 (3H) (s, C₅Me₄), 3.24 (m, 1H, HC₅),

4.73 (m, 1H, SiH). MS electron impact (m/e (relative

intensity)): 214 (18) [M⁺], 122 (100) [M⁺ꢀ Et(H)SiCl],

91 (52) [M⁺ꢀ C₅HMe₄].

5.3. Et(H)Si(C₅HMe₄)(C₅H₅)₂(3)

5. Experimental

From Et(H)Si(C₅HMe₄)Cl (2) (2.00 g, 9.31 mmol)

and Na(C₅H₅) (0.82 g, 9.31 mmol). Yield: 2.05 g, 90%.

¹H NMR (400 MHz, CDCl₃) (for the predominant iso-

mer): d ꢀ0.48 (2H), 0.95 (3H) (m, SiEt), 1.88 (3H),

1.90 (3H), 1.96 (3H), 2.07 (3H) (s, C₅Me₄), 2.90 (1H),

3.01 (1H) (m, HC₅), 3.42 (m, 1H, SiH), 6.57 (1H), 6.59

(1H), 6.66 (1H), 6.83 (1H) (m, C₅H₄). MS electron im-

pact (m/e (relative intensity)): 244 (18) [M⁺], 215 (28)

[M⁺ꢀ Et], 179 (100) [M⁺ꢀ C₅H₅], 123 (52)

[M⁺ꢀ C₅HMe₄], 121 (41) [M⁺ꢀ Et(H)SiC₅H₅].

All reactions were performed using standard

Schlenk tube techniques in an atmosphere of dry

nitrogen. Solvents were distilled from the appropriate

drying agents and degassed before use. C₅H₂Me₄,

[TiCl₄(THF)₂], ZrCl₄, HfCl₄, HSiMeCl₂,Si(CH@CH₂)₄,

SiMe₂(CH@ CH₂)₂and HSiEt₃were purchased from

Aldrich, HSiEtCl₂and HSiPhCl₂from Fluka and

HSi(CH₂CH@ CH₂)Cl₂and the Karstedt catalyst

from ABCR. All the commercial reagents were used

directly. Na(C₅H₅) [18], 27a, 27b and 28b [8e] were

prepared as previously described. IR spectra were re-

corded on a Thermo Nicolet Avatar 330 FT-IR spec-

trophotometer. ¹H, ¹³C and ²⁹Si NMR spectra were

recorded on a Varian Mercury FT-400 spectrometer.

Microanalyses were carried out with a Perkin–Elmer

2400 or LECO CHNS-932 microanalyser. Mass spec-

troscopic analyses were preformed on a Hewlett–Pack-

ard 5988A (m/z 50–1000) instrument. Polymer

molecular weights and distribution were determined

by GPC (Waters 150C Plus or Alliance GPC-2000)

in 1,2,4-trichlorobenzene at 150 ꢁC.

5.4. Ph(H)Si(C₅HMe₄)Cl (4)

From Ph(H)SiCl₂(6.92 g, 39.00 mmol) and

Li(C₅HMe₄) (2.50 g, 19.50 mmol). Yield: 4.66 g, 91%.

¹H NMR (400 MHz, CDCl₃) (for the predominant iso-

mer): d 1.63 (3H), 1.68 (3H), 1.96 (3H), 2.02 (3H) (s,

C₅Me₄), 3.43 (m, 1H, HC₅), 5.14 (m, 1H, SiH), 7.30

(2H), 7.38 (2H), 7.74 (1H) (m, SiPh). MS electron im-

pact (m/e (relative intensity)): 262 (74) [M⁺], 227 (26)

[M⁺ꢀ Cl], 141 (23) [M⁺ꢀ C₅HMe₄], 122 (100)

[M⁺ꢀ Ph(H)SiCl].

5.1. Synthesis of Et(H)Si(C₅H₅)₂(1)

5.5. Ph(H)Si(C₅HMe₄)(C₅H₅)₂(5)

Et(H)SiCl₂(3.66 g, 28.38 mmol) was added to a

solution of Na(C₅H₅) (5.00 g, 56.76 mmol) in THF

(50 mL) at ꢀ78 ꢁC. The reaction mixture was allowed

to warm to room temperature and stirred for 15 h.

Solvent was removed in vacuo and hexane (150 mL)

was added to the resulting orange oil. The mixture

From Ph(H)Si(C₅HMe₄)Cl (4) (2.00 g, 7.61 mmol)

and Na(C₅H₅) (0.67 g, 7.61 mmol). Yield: 1.96 g, 88%.

¹H NMR (400 MHz, CDCl₃) (for the predominant iso-

mer): d 1.65 (3H), 1.71 (3H), 1.72 (3H), 1.91 (3H) (s,

C₅Me₄), 3.06 (1H), 3.13 (1H) (m, HC₅), 3.60 (m, 1H,

´

S. Gomez-Ruiz et al. / Polyhedron 24 (2005) 1298–1313

1306

SiH), 6.63 (1H), 6.67 (1H), 6.73 (1H), 6.95 (1H) (m,

C₅H₄), 7.29 (2H), 7.33 (2H), 7.46 (1H) (m, SiPh). MS

electron impact (m/e (relative intensity)): 292 (24)

[M⁺], 262 (28) [M⁺ꢀ 2 · Me], 227 (100) [M⁺ꢀ C₅H₅],

171 (55) [M⁺ꢀ C₅HMe₄].

[M⁺ꢀ CH₂CH@CH₂, ꢀC₅HMe₄], 121 (98) [M⁺ꢀ CH₂CH@

CH₂(H)SiC₅HMe₄].

5.10. Synthesis of Li₂{Et(H)Si(C₅H₄)₂} (10)

LiBuⁿ(1.6 M in hexane) (13.3 mL, 21.24 mmol) was

added dropwise to a solution of Et(H)Si(C₅H₅)₂(1)

(2.00 g, 10.62 mmol) in hexane (100 mL) at ꢀ78 ꢁC. The

mixture was allowed to warm to 25 ꢁC and stirred for

15 h. Solvent was removed in vacuo to give a white solid

which was washed with hexane (2 · 50 mL) and dried un-

der vacuum to yield a free ﬂowing white solid of the title

complex (2.06 g, 97%). Anal. Calc. for C₁₂H₁₄Li₂Si: C,

71.99; H, 7.05. Found: C, 71.58; H, 7.00%.

5.6. Ph(H)Si(C₅HMe₄)₂(6)

From Ph(H)SiCl₂(1.73 g, 9.75 mmol) and Li(C₅H-

Me₄) (2.50 g, 19.50 mmol). Yield: 2.05 g, 90%. ¹H

NMR (400 MHz, CDCl₃) (for the predominant isomer):

d 1.62 (6H), 1.68 (6H), 1.85 (6H), 1.99 (6H) (s, C₅Me₄),

3.27 (m, 2H, HC₅), 4.06 (m, 1H, SiH), 7.03 (2H), 7.17

(2H), 7.22 (1H) (m, SiPh). MS electron impact (m/e

(relative intensity)): 348 (9) [M⁺], 227 (100)

[M⁺ꢀ C₅HMe₄], 121 (14) [M⁺ꢀ Ph(H)SiC₅HMe₄],

105 (17) [M⁺ꢀ 2 · C₅HMe₄].

The preparation of 11–15 was carried out in an iden-

tical manner to 10.

5.11. Li₂{Et(H)Si(C₅Me₄)(C₅H₄)} (11)

5.7. CH₂@CHCH₂(H)Si(C₅HMe₄)Cl (7)

From

Et(H)Si(C₅HMe₄)(C₅H₅)₂

(3)

(2.00 g,

8.18 mmol) and LiBuⁿ(1.6 M in hexane) (10.2 mL,

16.36 mmol). Yield: 1.89 g, 90%. Anal. Calc. for

C₁₆H₂₂Li₂Si: C, 74.98; H, 8.65. Found: C, 74.49; H,

8.60%.

From CH₂@CHCH₂(H)SiCl₂(2.74 g, 19.50 mmol)

and Li(C₅HMe₄) (2.50 g, 19.50 mmol). Yield: 3.57 g,

1

94%. H NMR (400 MHz, CDCl₃) (for the predomi-

nant isomer): d 1.52 (m, 2H, CH₂CH@CH₂), 1.81

(6H), 1.82 (3H), 1.86 (3H) (s, C₅Me₄), 2.74 (m, 1H,

HC₅), 4.77 (m, 1H, SiH), 4.93 (m, 2H,

CH₂CH@CH₂), 5.59 (m, 1H, CH₂CH@CH₂). MS

electron impact (m/e (relative intensity)): 226 (1)

[M⁺], 121 (100) [M⁺ꢀ CH₂CH@ CH₂(H)SiCl], 103

(46) [M⁺ꢀ C₅HMe₄].

5.12. Li₂{Ph(H)Si(C₅Me₄)(C₅H₄)} (12)

From

Ph(H)Si(C₅HMe₄)(C₅H₅)₂

(5)

(2.00 g,

6.83 mmol) and LiBuⁿ(1.6 M in hexane) (8.6 mL,

13.66 mmol). Yield: 1.83 g, 88%. Anal. Calc. for

C₂₀H₂₂Li₂Si: C, 78.93; H, 7.29. Found: C, 78.66; H,

7.27%.

5.8. CH₂@CHCH₂(H)Si(C₅HMe₄)(C₅H₅) (8)

From CH₂@CHCH₂(H)Si(C₅HMe₄)Cl (7) (2.00 g,

8.81 mmol) and Na(C₅H₅) (0.78 g, 8.81 mmol). Yield:

5.13. Li₂{Ph(H)Si(C₅Me₄)₂} (13)

1

1.78 g, 79%. H NMR (400 MHz, CDCl₃) (for the pre-

From Ph(H)Si(C₅HMe₄)₂(6) (2.00 g, 5.73 mmol) and

LiBuⁿ(1.6 M in hexane) (7.2 mL, 11.46 mmol). Yield:

1.69 g, 82%. Anal. Calc. for C₂₄H₃₀Li₂Si: C, 79.97; H,

8.39. Found: C, 79.45; H, 8.31%.

dominant isomer): d 1.50 (m, 2H, CH₂CH@CH₂), 1.66

(3H), 1.74 (3H), 1.80 (3H), 1.91 (3H) (s, C₅Me₄), 2.73

(1H), 3.03 (1H) (m, HC₅), 4.64 (m, 1H, SiH), 4.94 (m,

2H, CH₂CH@CH₂), 6.49 (m, 1H, CH₂CH@CH₂), 5.95

(2H), 6.41 (2H), (m, C₅H₄). MS electron impact (m/e

(relative intensity)): 256 (5) [M⁺], 215 (7) [M⁺ꢀ

CH₂CH@CH₂], 191 (19) [M⁺ꢀ C₅H₅], 149 (100)

[M⁺ꢀ CH₂CH@CH₂, ꢀC₅H₅, ꢀH].

5.14. Li₂{CH₂@CHCH₂(H)Si(C₅Me₄)(C₅H₄)} (14)

From CH₂@CHCH₂(H)Si(C₅HMe₄)(C₅H₅) (8) (2.00 g,

7.80 mmol) and LiBuⁿ(1.6 M in hexane) (9.8 mL,

15.60 mmol). Yield: 1.73 g, 83%. Anal. Calc. for

C₁₇H₂₂Li₂Si: C, 76.10; H, 8.26. Found: C, 75.89; H,

8.22%.

5.9. CH₂@CHCH₂(H)Si(C₅HMe₄)₂(9)

From CH₂@CHCH₂(H)SiCl₂(1.37 g, 9.75 mmol)

and Li(C₅HMe₄) (2.50 g, 19.50 mmol). Yield: 2.86 g,

94%. ¹H NMR (400 MHz, CDCl₃) (for the predominant

isomer): d 1.48 (m, 2H, CH₂CH@CH₂), 1.83 (12H), 1.92

(6H), 1.97 (6H) (s, C₅Me₄), 2.70 (m, 2H, HC₅), 3.98 (m,

1H, SiH), 4.88 (m, 2H, CH₂CH@CH₂), 5.67 (m, 1H,

CH₂CH@CH₂). MS electron impact (m/e (relative inten-

sity)): 312 (21) [M⁺], 191 (85) [M⁺ꢀ C₅HMe₄], 149 (100)

5.15. Li₂{CH₂@CHCH₂(H)Si(C₅Me₄)₂} (15)

From CH₂@CHCH₂(H)Si(C₅HMe₄)₂(9) (2.00 g, 6.40

mmol) and LiBuⁿ(1.6 M in hexane) (8.0 ml,

12.80 mmol). Yield: 1.70 g, 78%. Anal. Calc. for

C₂₁H₃₀Li₂Si: C, 77.74; H, 9.32. Found: C, 77.44; H,

9.28%.

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S. Gomez-Ruiz et al. / Polyhedron 24 (2005) 1298–1313

1307

5.16. Synthesis of [Ti{Et(H)Si(g⁵-C₅H₄)₂}Cl₂] (16a)

5.19. [Ti{Et(H)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (17a)

THF (50 mL) was added to a solid mixture of

[TiCl₄(THF)₂] (1.67 g, 4.99 mmol) and Li₂{Et(H)Si(g⁵-

C₅H₄)₂} (10) (1.00 g, 4.99 mmol). The resulting solution

was stirred for 15 h. Solvent was removed in vacuo and

toluene added (75 mL) to the resulting solid. The mix-

ture was ﬁltered and the ﬁltrate concentrated (10 mL)

and cooled to ꢀ30 ꢁC to yield crystals of the title com-

From [TiCl₄(THF)₂] (1.30 g, 3.90 mmol) and

Li₂{Et(H)Si(C₅Me₄)(C₅H₄)} (11) (1.00 g, 3.90 mmol).

Yield: 0.89 g, 63%. IR (ZnSe): m_Si–H2172 cm^{ꢀ1 1}H

.

NMR (400 MHz, CDCl₃): d 1.38 (3H), 1.48 (2H) (m,

SiEt), 1.87 (3H), 1.90 (3H), 2.15 (3H), 2.16 (3H) (s,

C₅Me₄), 5.21 (dd, 1H, SiH) (³J(¹H–¹H) 4.4 Hz), 5.59

(1H), 5.62 (1H), 7.17 (1H), 7.22 (1H) (m, C₅H₄).

¹³C{¹H} NMR (100 MHz, CDCl₃): d 3.3, 7.8 (SiEt),

13.7, 15.7, 15.8 (C₅Me₄), 95.3 (C^ipso), 115.2, 117.0,

132.3, 134.3 (C₅H₄), 99.7, 129.8, 131.7, 144.0, 144.5

(C₅Me₄). ²⁹Si NMR (79.49 MHz, CDCl₃): d ꢀ25.5 (dou-

blet of multiplets) (¹J(²⁹Si–¹H) 210.6 Hz). MS electron

impact (m/e (relative intensity)): 360 (48) [M⁺], 324

(100) [M⁺ꢀ Cl, –H], 288 (91) [M⁺ꢀ 2 · Cl, ꢀH]. Anal.

Calc. for C₁₆H₂₂Cl₂SiTi: C, 53.20; H, 6.14. Found: C,

53.01; H, 6.09%.

plex (0.78 g, 51%). IR (ZnSe): m_Si–H2187 cm^{ꢀ1 1}H

.

NMR (400 MHz, CDCl₃): d 1.11 (3H), 1.37 (2H) (m,

SiEt), 5.05 (t, 1H, SiH) (³J(¹H–¹H) 3.3 Hz), 6.02 (2H),

6.08 (2H), 7.22 (2H), 7.25 (2H) (m, C₅H₄). ¹³C{¹H}

NMR (100 MHz, CDCl₃): d 1.5, 7.3 (SiEt), 101.7 (C^ipso),

118.2, 120.4, 134.7, 136.2 (C₅H₄). ²⁹Si NMR

(79.49 MHz, CDCl₃): d ꢀ24.0 (doublet of multiplets)

(¹J(²⁹Si–¹H) 214.7 Hz). MS electron impact (m/e (rela-

tive intensity)): 304 (74) [M⁺], 268 (32) [M⁺ꢀ Cl], 240

(37) [M⁺ꢀ Cl, ꢀEt], 176 (100) [M⁺ꢀ Cl, ꢀEt,

ꢀC₅H₄]. Anal. Calc. for C₁₂H₁₄Cl₂SiTi: C, 47.24; H,

4.63. Found: C, 47.11; H, 4.59%.

5.20. [Zr{Et(H)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (17b)

The preparation of 16b–32 was carried out in an iden-

tical manner to 16a.

From ZrCl₄(0.91 g, 3.90 mmol) and Li₂{Et(H)-

Si(C₅Me₄)(C₅H₄)} (11) (1.00 g, 3.90 mmol). Yield:

0.73 g, 46%. IR (ZnSe): m_Si–H2168 cm^{ꢀ1 1}H NMR

.

5.17. [Zr{Et(H)Si(g⁵-C₅H₄)₂}Cl₂] (16b)

(400 MHz, CDCl₃): d 1.36 (3H), 1.46 (2H) (m, SiEt),

2.03 (3H), 2.07 (3H), 2.08 (6H) (s, C₅Me₄), 5.20 (dd,

1H, SiH) (³J(¹H–¹H) 4.4 Hz), 5.71 (1H), 5.78 (1H),

6.99 (1H), 7.04 (1H) (m, C₅H₄). ¹³C{¹H} NMR

(100 MHz, CDCl₃): d 3.6, 7.9 (SiEt), 12.3, 12.4, 14.4,

14.9 (C₅Me₄), 95.1 (C^ipso), 112.1, 113.9, 126.4, 127.8

(C₅H₄), 102.5, 124.7, 126.0, 135.7, 136.2 (C₅Me₄).

²⁹Si NMR (79.49 MHz, CDCl₃): d ꢀ26.7 (doublet of

multiplets) (¹J(²⁹Si–¹H) 207.6 Hz). MS electron impact

(m/e (relative intensity)): 402 (88) [M⁺], 366 (100)

[M⁺ꢀ Cl], 338 (86) [M⁺ꢀ Cl, ꢀEt]. Anal. Calc. for

C₁₆H₂₂Cl₂SiZr: C, 47.50; H, 5.48. Found: C, 47.33;

H, 5.48%.

From ZrCl₄(1.16 g, 4.99 mmol) and Li₂{Et(H)-

Si(C₅H₄)₂} (10) (1.00 g, 4.99 mmol). Yield: 0.63 g,

1

36%. IR (ZnSe): m_Si–H2177 cm^ꢀ1. H NMR (400 MHz,

CDCl₃): d 1.17 (3H), 1.37 (2H) (m, SiEt), 5.07 (t, 1H,

SiH) (³J(¹H–¹H) 3.3 Hz), 6.02 (2H), 6.11 (2H), 6.97

(2H), 7.00 (2H) (m, C₅H₄). ¹³C{¹H} NMR (100 MHz,

CDCl₃): d 1.7, 7.3 (SiEt), 104.6 (C^ipso), 113.7, 116.0,

127.8, 129.3 (C₅H₄). ²⁹Si NMR (79.49 MHz, CDCl₃): d

ꢀ24.2 (doublet of multiplets) (¹J(²⁹Si–¹H) 213.4 Hz).

MS electron impact (m/e (relative intensity)): 348 (70)

[M⁺], 316 (25) [M⁺ꢀ Et], 282 (39) [M⁺ꢀ Cl, ꢀEt],

253 (45) [M⁺ꢀ Et, ꢀC₅H₄]. Anal. Calc. for

C₁₂H₁₄Cl₂SiZr: C, 41.36; H, 4.05. Found: C, 41.05; H,

4.04%.

5.21. [Hf{Et(H)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (17c)

From HfCl₄(1.25 g, 3.90 mmol) and Li₂{Et(H)Si-

(C₅Me₄)(C₅H₄)} (11) (1.00 g, 3.90 mmol). Yield: 0.82 g,

5.18. [Hf{Et(H)Si(g⁵-C₅H₄)₂}Cl₂] (16c)

1

43%. IR (ZnSe): m_Si–H2164 cm^ꢀ1. H NMR (400 MHz,

From HfCl₄(1.60 g, 4.99 mmol) and Li₂{Et(H)-

Si(C₅H₄)₂} (10) (1.00 g, 4.99 mmol). Yield: 0.67 g,

CDCl₃): d 1.34 (3H), 1.45 (2H) (m, SiEt), 2.03 (3H),

2.07 (3H), 2.08 (6H) (s, C₅Me₄), 5.18 (dd, 1H, SiH)

(³J(¹H–¹H) 4.4 Hz), 5.67 (1H), 5.73 (1H), 6.91 (1H),

6.97 (1H) (m, C₅H₄). ¹³C{¹H} NMR (100 MHz,

CDCl₃): d 3.6, 7.8 (SiEt), 12.1, 12.2, 14.0, 14.5

(C₅Me₄), 97.0 (C^ipso), 109.5, 111.5, 125.0, 126.9 (C₅H₄),

104.6, 121.5, 123.3, 133.8, 134.3 (C₅Me₄). ²⁹Si NMR

(79.49 MHz, CDCl₃): d ꢀ27.3 (doublet of multiplets)

(¹J(²⁹Si–¹H) 207.2 Hz). MS electron impact (m/e (rela-

tive intensity)): 492 (85) [M⁺], 456 (100) [M⁺ꢀ Cl,

ꢀH], 428 (19) [M⁺ꢀ Cl, ꢀEt]. Anal. Calc. for

C₁₆H₂₂Cl₂HfSi: C, 39.07; H, 4.51. Found: C, 39.00; H,

4.46%.

1

31%. IR (ZnSe): m_Si–H2166 cm^ꢀ1. H NMR (400 MHz,

CDCl₃): d 1.11 (3H), 1.36 (2H) (m, SiEt), 5.06 (t, 1H,

SiH) (³J(¹H–¹H) 3.3 Hz), 5.95 (2H), 6.03 (2H), 6.88

(2H), 6.90 (2H) (m, C₅H₄). ¹³C{¹H} NMR (100 MHz,

CDCl₃): d 1.8, 7.5 (SiEt), 106.1 (C^ipso), 111.5, 113.9,

126.4, 127.9 (C₅H₄). ²⁹Si NMR (79.49 MHz, CDCl₃): d

ꢀ24.9 (doublet of multiplets) (¹J(²⁹Si–¹H) 215.1 Hz).

MS electron impact (m/e (relative intensity)): 436 (26)

[M⁺], 407 (16) [M⁺ꢀ Et], 250 (65) [M⁺ꢀ Et(H)-

Si(C₅H₄)₂]. Anal. Calc. for C₁₂H₁₄Cl₂HfSi: C, 33.08;

H, 3.24. Found: C, 32.99; H, 3.19%.

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S. Gomez-Ruiz et al. / Polyhedron 24 (2005) 1298–1313

1308

5.22. [Ti{Ph(H)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (18a)

Hf(C₅H₄Si(H)Ph)Cl₂]. Anal. Calc. for C₂₀H₂₂Cl₂HfSi:

C, 44.49; H, 4.11. Found: C, 44.03; H, 4.08%.

From [TiCl₄(THF)₂] (1.10 g, 3.28 mmol) and

Li₂{Ph(H)Si(C₅Me₄)(C₅H₄)} (12) (1.00 g, 3.28 mmol).

.

Yield: 0.82 g, 61%. IR (ZnSe): m_Si–H2167 cm^{ꢀ1 1}H

5.25. [Ti{Ph(H)Si(g⁵-C₅Me₄)₂}Cl₂] (19a)

NMR (400 MHz, CDCl₃): d 1.49 (3H), 2.00 (3H), 2.11

(3H), 2.22 (3H) (s, C₅Me₄), 5.85 (s, 1H, SiH), 5.68

(1H), 5.81 (1H), 7.21 (2H) (m, C₅H₄), 7.31 (2H), 7.55

(2H), 7.95 (1H) (m, SiPh). ¹³C{¹H} NMR (100 MHz,

CDCl₃): d 13.5, 13.8, 15.9, 16.8 (C₅Me₄), 94.5 (C^ipso),

115.2, 118.0, 134.7, 135.9 (C₅H₄), 98.4, 128.5, 129.8,

143.0, 146.0 (C₅Me₄), 128.8, 130.9, 131.2, 133.1 (SiPh).

From [TiCl₄(THF)₂] (0.92 g, 2.77 mmol) and

Li₂{Ph(H)Si(C₅Me₄)₂} (13) (1.00 g, 2.77 mmol). Yield:

0.80 g, 62%. IR (ZnSe): m_Si–H2155 cm^{ꢀ1 1}H NMR

.

(400 MHz, CDCl₃): d 1.59 (6H), 1.93 (6H), 2.11

(6H), 2.18 (6H) (s, C₅Me₄), 6.06 (s, 1H, SiH), 7.26

(2H), 7.53 (2H), 7.98 (1H) (m, SiPh). ¹³C{¹H} NMR

(100 MHz, CDCl₃): d 13.9, 16.1, 17.2 (C₅Me₄), 88.4,

125.2, 130.8, 143.2, 144.5 (C₅Me₄), 128.1, 128.4,

130.9, 135.0 (SiPh). ²⁹Si NMR (79.49 MHz, CDCl₃):

d ꢀ41.3 (d) (¹J(²⁹Si–¹H) 210.1 Hz). MS electron im-

pact (m/e (relative intensity)): 464 (12) [M⁺], 428 (22)

[M⁺ꢀ Cl], 413 (25) [M⁺ꢀ Cl, ꢀMe], 105 (100)

[M⁺ꢀ Ti(C₅Me₄)₂Cl₂]. Anal. Calc. for C₂₄H₃₀Cl₂SiTi:

C, 61.94; H, 6.50. Found: C, 61.55; H, 6.42%.

²⁹Si NMR (79.49 MHz, CDCl₃):

d

ꢀ32.4 (d)

(¹J(²⁹Si–¹H) 215.4 Hz). MS electron impact (m/e (relative

intensity)): 408 (26) [M⁺], 372 (41) [M⁺ꢀ Cl, ꢀH], 336

(100) [M⁺ꢀ 2 · Cl, ꢀH]. Anal. Calc. for C₂₀H₂₂Cl₂SiTi:

C, 58.70; H, 5.42. Found: C, 58.44; H, 5.34%.

5.23. [Zr{Ph(H)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (18b)

5.26. [Zr{Ph(H)Si(g⁵-C₅Me₄)₂}Cl₂] (19b)

From ZrCl₄(0.77 g, 3.28 mmol) and Li₂{Ph(H)-

Si(C₅Me₄)(C₅H₄)} (12) (1.00 g, 3.28 mmol). Yield:

0.82 g, 55%. IR (ZnSe): m_Si–H2155 cm^{ꢀ1 1}H NMR

.

From ZrCl₄(0.67 g, 2.77 mmol) and Li₂{Ph(H)-

Si(C₅Me₄)₂} (13) (1.00 g, 2.77 mmol). Yield: 0.66 g,

(400 MHz, CDCl₃): d 1.60 (3H), 2.04 (3H), 2.12

(3H), 2.13 (3H) (s, C₅Me₄), 5.88 (s, 1H, SiH), 5.81

(1H), 5.98 (1H), 7.05 (1H), 7.13 (1H) (m, C₅H₄),

7.28 (2H), 7.57 (2H), 7.95 (1H) (m, SiPh). ¹³C{¹H}

NMR (100 MHz, CDCl₃): d 12.3, 12.4, 14.5, 15.1

(C₅Me₄), 94.2 (C^ipso), 125.0, 128.7, 134.6, 135.1

(C₅H₄), 101.0, 112.2, 114.7, 128.9, 131.0 (C₅Me₄),

124.4, 128.6, 129.0, 134.2 (SiPh). ²⁹Si NMR

47%. IR (ZnSe): m_Si–H2169 cm^ꢀ1

.

¹H NMR

(400 MHz, CDCl₃): d 1.70 (6H), 2.04 (6H), 2.07

(6H), 2.13 (6H) (s, C₅Me₄), 6.02 (s, 1H, SiH), 7.26

(2H), 7.52 (2H), 7.94 (1H) (m, SiPh). ¹³C{¹H} NMR

(100 MHz, CDCl₃): d 12.6, 12.7, 14.9, 16.1 (C₅Me₄),

89.0, 124.9, 125.2, 136.0, 136.9 (C₅Me₄), 128.3,

130.3, 130.7, 135.0 (SiPh). ²⁹Si NMR (79.49 MHz,

CDCl₃): d ꢀ43.0 (d) (¹J(²⁹Si–¹H) 208.5 Hz). MS elec-

tron impact (m/e (relative intensity)): 508 (86) [M⁺],

471 (40) [M⁺ꢀ Cl], 455 (89) [M⁺ꢀ Cl, ꢀMe], 105

(79.49 MHz, CDCl₃):

d

ꢀ37.9 (d) (¹J(²⁹Si–¹H)

214.5 Hz). MS electron impact (m/e (relative inten-

sity)): 452 (34) [M⁺], 414 (57) [M⁺ꢀ Cl, ꢀH], 105

(100) [M⁺ꢀ H, ꢀZr(C₅Me₄)(C₅H₄)Cl₂]. Anal. Calc.

for C₂₀H₂₂Cl₂SiZr: C, 53.07; H, 4.90. Found: C,

52.96; H, 4.87%.

(100)

[M⁺ꢀ Zr(C₅Me₄)₂Cl₂].

Anal.

Calc.

for

C₂₄H₃₀Cl₂SiZr: C, 56.66; H, 5.94. Found: C, 56.12;

H, 5.91%.

5.24. [Hf{Ph(H)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (18c)

5.27. [Hf{Ph(H)Si(g⁵-C₅Me₄)₂}Cl₂] (19c)

From HfCl₄(1.05 g, 3.28 mmol) and Li₂{Ph(H)-

Si(C₅Me₄)(C₅H₄)} (12) (1.00 g, 3.28 mmol). Yield:

From HfCl₄(0.89 g, 2.77 mmol) and Li₂{Ph(H)-

Si(C₅Me₄)₂} (13) (1.00 g, 2.77 mmol). Yield: 0.64 g,

0.74 g, 42%. IR (ZnSe): m_Si–H2172 cm^ꢀ1

.

¹H NMR

39%. IR (ZnSe): m_Si–H2116 cm^ꢀ1

.

¹H NMR

(400 MHz, CDCl₃): d 1.66 (3H), 2.06 (3H), 2.13

(3H), 2.19 (3H) (s, C₅Me₄), 5.84 (s, 1H, SiH), 5.77

(1H), 5.93 (1H), 6.98 (1H), 7.06 (1H) (m, C₅H₄),

7.27 (2H), 7.55 (2H), 7.95 (1H) (m, SiPh). ¹³C{¹H}

NMR (100 MHz, CDCl₃): d 12.1, 12.2, 14.2, 14.8

(C₅Me₄), 95.9 (C^ipso), 109.7, 112.5, 128.2, 130.9

(C₅H₄), 103.1, 121.6, 124.2, 133.3, 135.6 (C₅Me₄),

124.4, 128.6, 129.0, 134.2 (SiPh). ²⁹Si NMR

(400 MHz, CDCl₃): d 1.77 (6H), 2.09 (6H), 2.12

(6H), 2.16 (6H) (s, C₅Me₄), 5.99 (s, 1H, SiH), 7.18

(2H), 7.50 (2H), 7.95 (1H) (m, SiPh). ¹³C{¹H} NMR

(100 MHz, CDCl₃): d 12.5, 12.6, 14.8, 16.0 (C₅Me₄),

91.1, 121.8, 123.4, 134.3, 135.3 (C₅Me₄), 128.2,

130.3, 130.5, 134.9 (SiPh). ²⁹Si NMR (79.49 MHz,

CDCl₃): d ꢀ43.7 (d) (¹J(²⁹Si–¹H) 208.7 Hz). MS elec-

tron impact (m/e (relative intensity)): 596 (29) [M⁺],

561 (3) [M⁺ꢀ Cl], 545 (12) [M⁺ꢀ Cl, ꢀMe], 105

(79.49 MHz, CDCl₃):

d

ꢀ38.5 (d) (¹J(²⁹Si–¹H)

214.1 Hz). MS electron impact (m/e (relative inten-

sity)): 540 (9) [M⁺], 502 (6) [M⁺ꢀ Cl], 315 (5)

[M⁺ꢀ Ph(H)Si(C₅Me₄)(C₅H₄)], 123 (100) [M⁺ꢀ

(100)

[M⁺ꢀ Hf(C₅Me₄)₂Cl₂].

Anal.

Calc.

for

C₂₄H₃₀Cl₂HfSi: C, 48.37; H, 5.07. Found: C, 48.00;

H, 5.02%.

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S. Gomez-Ruiz et al. / Polyhedron 24 (2005) 1298–1313

1309

5.28. [Ti{CH₂@CHCH₂(H)Si(g⁵-C₅Me₄)-

(g⁵-C₅H₄)}Cl₂] (20a)

1.83 (6H), 1.87 (6H), 2.12 (12H) (s, C₅Me₄), 2.59 (m,

2H, CH₂CH@CH₂), 5.37 (t, 1H, SiH) (³J(¹H–¹H)

5.2 Hz), 5.17 (1H) (cis), 5.28 (1H) (trans) (dd,

CH₂CH@CH₂) (³J_cis(¹H–¹H) 9.9, ³J_trans(¹H–¹H)

16.9 Hz), 6.10 (m, 1H, CH₂CH@CH₂). ¹³C{¹H} NMR

(100 MHz, CDCl₃): d 13.7, 13.9, 16.0, 16.7 (C₅Me₄),

19.5 (CH₂CH@CH₂), 89.5, 129.0, 130.0, 143.4, 143.6

(C₅Me₄), 116.7 (CH₂CH@CH₂), 131.6 (CH₂CH@CH₂).

²⁹Si NMR (79.49 MHz, CDCl₃): d ꢀ34.7 (doublet of

multiplets) (¹J(²⁹Si–¹H) 213.9 Hz). MS electron impact

(m/e (relative intensity)): 428 (78) [M⁺], 392 (100)

[M⁺ꢀ Cl], 387 (44) [M⁺ꢀ CH₂CH@CH₂], 351 (22)

[M⁺ꢀ Cl, ꢀCH₂CH@CH₂]. Anal. Calc. for C₂₁H₃₀-

Cl₂SiTi: C, 58.75; H, 7.04. Found: C, 58.52; H, 7.01%.

From [TiCl₄(THF)₂] (1.24 g, 3.73 mmol) and

Li₂{CH₂@CHCH₂(H)Si(C₅Me₄)(C₅H₄)} (14) (1.00 g,

3.73 mmol). Yield: 0.85 g, 61%. IR (ZnSe): m_Si–H2166,

m_CH3081, m_CH@CH1625 cm^ꢀ1

.

¹H NMR (400 MHz,

2

CDCl₃): d 1.90 (6H), 2.16 (6H) (s, C₅Me₄), 2.47 (m,

2H, CH₂CH@CH₂), 5.23 (dd, 1H, SiH) (³J(¹H–¹H)

4.4 Hz), 5.17 (1H) (cis), 5.26 (1H) (trans) (dd,

CH₂CH@CH₂) (³J_cis(¹H–¹H) 10.0, ³J_trans(¹H–¹H)

17.1 Hz), 6.06 (m, 1H, CH₂CH@CH₂), 5.63 (1H), 6.06

(1H), 7.18 (1H), 7.24 (1H) (m, C₅H₄). ¹³C{¹H} NMR

(100 MHz, CDCl₃): d 13.8, 15.8, 16.5 (C₅Me₄), 18.1

(CH₂CH@CH₂), 95.0 (C^ipso), 115.1, 116.9, 132.1, 134.4

(C₅H₄), 95.2, 129.5, 130.7, 143.8, 144.5 (C₅Me₄), 117.1

(CH₂CH@CH₂), 131.6 (CH₂CH@CH₂). ²⁹Si NMR

(79.49 MHz, CDCl₃): d ꢀ30.0 (doublet of multiplets)

(¹J(²⁹Si–¹H) 217.0 Hz). MS electron impact (m/e (rela-

tive intensity)): 372 (48) [M⁺], 336 (100) [M⁺ꢀ Cl,

ꢀH], 295 (44) [M⁺ꢀ Cl, ꢀH, ꢀCH₂CH@CH₂], 123

(100) [M⁺ꢀ Ti(C₅H₄Si(H)CH₂CH@CH₂)Cl₂]. Anal.

Calc. for C₁₇H₂₂Cl₂SiTi: C, 54.71; H, 5.94. Found: C,

54.35; H, 5.94%.

5.31. [Zr{CH₂@CHCH₂(H)Si(g⁵-C₅Me₄)₂}Cl₂] (21b)

From ZrCl₄(0.68 g, 2.93 mmol) and Li₂{CH₂@

CHCH₂(H)Si(C₅Me₄)₂} (15) (1.00 g, 2.93 mmol). Yield:

0.72 g, 52%. IR (ZnSe): m_Si–H2182, m_CH3076,

m_CH@CH1631 cm^ꢀ1

.

¹H NMR (400 MHz, CDCl₃): d

2

1.93 (6H), 1.97 (6H), 2.07 (12H) (s, C₅Me₄), 2.55 (m,

2H, CH₂CH@CH₂), 5.34 (t, 1H, SiH) (³J(¹H–¹H)

5.2 Hz), 5.14 (1H) (cis), 5.25 (1H) (trans) (dd,

CH₂CH@CH₂) (³J_cis(¹H–¹H) 10.0, ³J_trans(¹H–¹H)

17.0 Hz), 6.07 (m, 1H, CH₂CH@CH₂). ¹³C{¹H} NMR

(100 MHz, CDCl₃): d 12.5, 12.7, 14.8, 15.6 (C₅Me₄),

19.9 (CH₂CH@CH₂), 90.3, 124.5, 125.5, 136.0, 136.2

(C₅Me₄), 116.5 (CH₂CH@CH₂), 131.8 (CH₂CH@CH₂).

²⁹Si NMR (79.49 MHz, CDCl₃): d ꢀ36.0 (doublet of

multiplets) (¹J(²⁹Si–¹H) 209.2 Hz). MS electron impact

(m/e (relative intensity)): 472 (80) [M⁺], 435 (44)

[M⁺ꢀ Cl], 419 (100) [M⁺ꢀ Cl, ꢀMe]. Anal. Calc. for

C₂₁H₃₀Cl₂SiZr: C, 53.36; H, 6.40. Found: C, 53.31; H,

6.39%.

5.29. [Zr{CH₂@CHCH₂(H)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}-

Cl₂] (20b)

From ZrCl₄(0.87 g, 3.73 mmol) and Li₂{CH₂@

CHCH₂(H)Si(C₅Me₄)(C₅H₄)} (14) (1.00 g, 3.73 mmol).

Yield: 0.79 g, 51%. IR (ZnSe): m_Si–H2170, m_CH3080,

m_CH@CH1626 cm^ꢀ1

.

¹H NMR (400 MHz, CDCl₃): d

2

2.00 (3H), 2.06 (3H), 2.07 (6H) (s, C₅Me₄), 2.45 (m,

2H, CH₂CH@CH₂), 5.22 (dd, 1H, SiH) (³J(¹H–¹H)

4.4 Hz), 5.14 (1H) (cis), 5.25 (1H) (trans) (dd,

CH₂CH@CH₂) (³J_cis(¹H–¹H) 10.1, ³J_trans(¹H–¹H)

17.1 Hz), 6.04 (m, 1H, CH₂CH@CH₂), 5.74 (1H), 5.78

(1H), 7.00 (2H) (m, C₅H₄). ¹³C{¹H} NMR (100 MHz,

5.32. [Hf{CH₂@CHCH₂(H)Si(g⁵-C₅Me₄)₂}Cl₂] (21c)

CDCl₃):

d

12.3, 13.9, 14.4, 15.1 (C₅Me₄), 18.3

From HfCl₄(0.94 g, 2.93 mmol) and Li₂{CH₂@

CHCH₂(H)Si(C₅Me₄)₂} (15) (1.00 g, 2.93 mmol). Yield:

0.71 g, 43%. IR (ZnSe): m_Si–H2165, m_CH3077,

(CH₂CH@CH₂), 94.9 (C^ipso), 112.0, 113.9, 125.9, 128.0

(C₅H₄), 102.0, 124.4, 126.4, 136.0, 136.3 (C₅Me₄),

116.9 (CH₂CH@CH₂), 131.1 (CH₂CH@CH₂). ²⁹Si

NMR (79.49 MHz, CDCl₃): d ꢀ31.1 (doublet of multi-

plets) (¹J(²⁹Si–¹H) 215.1 Hz). MS electron impact (m/e

(relative intensity)): 416 (22) [M⁺], 378 (23) [M⁺ꢀ Cl,

ꢀH], 337 (20) [M⁺ꢀ Cl, ꢀH, ꢀCH₂CH@CH₂], 303 (5)

[M⁺ꢀ 2 · Cl, ꢀH, ꢀCH₂CH@CH₂]. Anal. Calc. for

C₁₇H₂₂Cl₂SiZr: C, 49.01; H, 5.32. Found: C, 48.88; H,

5.28%.

m_CH@CH1629 cm^ꢀ1

.

¹H NMR (400 MHz, CDCl₃): d

2

2.01 (6 H), 2.04 (6H), 2.09 (6H), 2.10 (6H) (s, C₅Me₄),

2.54 (m, 2H, CH₂CH@CH₂), 5.30 (t, 1H, SiH)

(³J(¹H–¹H) 5.1 Hz), 5.13 (1H) (cis), 5.24 (1H) (trans)

3

(dd, CH₂CH@CH₂) (³J_cis(¹H–¹H) 10.0, J_trans(¹H–¹H)

17.1 Hz), 6.06 (m, 1H, CH₂CH@CH₂). ¹³C{¹H} NMR

(100 MHz, CDCl₃): d 12.4, 12.5, 14.6, 15.4 (C₅Me₄),

19.9 (CH₂CH@CH₂), 92.3, 121.6, 122.6, 134.5, 134.7

(C₅Me₄), 116.4 (CH₂CH@CH₂), 131.9 (CH₂CH@CH₂).

²⁹Si NMR (79.49 MHz, CDCl₃): d ꢀ36.6 (doublet of

multiplets) (¹J(²⁹Si–¹H) 208.9 Hz). MS electron impact

(m/e (relative intensity)): 560 (40) [M⁺], 519 (53)

[M⁺ꢀ CH₂CH@CH₂], 504 (20) [M⁺ꢀ Me, ꢀCH₂CH@

CH₂]. Anal. Calc. for C₂₁H₃₀Cl₂HfSi: C, 45.04; H, 5.40.

Found: C, 45.02; H, 5.36%.

5.30. [Ti{CH₂@CHCH₂(H)Si(g⁵-C₅Me₄)₂}Cl₂] (21a)

From [TiCl₄(THF)₂] (0.98 g, 2.93 mmol) and

Li₂{CH₂@CHCH₂(H)Si(C₅Me₄)₂} (15) (1.00 g, 2.93 mmol).

Yield: 0.81 g, 64%. IR (ZnSe): m_Si–H2169, m_CH3076,

m_CH@CH1627 cm^ꢀ1

.

¹H NMR (400 MHz, CDCl₃): d

2

´

S. Gomez-Ruiz et al. / Polyhedron 24 (2005) 1298–1313

1310

The experimental procedure described for 22–24 re-

lates to the optimized synthesis of the monohydrosilyla-

tion product.

(SiCH@CH₂), ꢀ7.8 (SiC₅H₄). MS electron impact

(m/e (relative intensity)): 496 (23) [M⁺], 460 (13)

[M⁺ꢀ Cl],

109

(C₅Me₄)(C₅H₄)}Cl₂]. Anal. Calc. for C₂₄H₃₄Cl₂Si₂Ti:

(100)

[M⁺ꢀ Ti{CH₂CH₂Si(Et)-

5.33. Synthesis of [Zr{(CH₂@CH)₃SiCH₂CH₂(Et)Si-

(g⁵-C₅H₄)₂}Cl₂] (22b)

C, 57.94; H, 6.89. Found: C, 57.88; H, 6.85%.

5.35. [Zr{(CH₂@CH)₃SiCH₂CH₂(Et)Si(g⁵-C₅Me₄)-

(g⁵-C₅H₄)}Cl₂] (23b)

Two drops of the Karstedt catalyst (divin-

yltetramethylsiloxane Pt(0) in xylene (3–3.5%)) were

added to

a solution of tetravinylsilane (0.059 g,

From Si(CH@CH₂)₄(0.051 g, 0.37 mmol) and

[Zr{Et(H)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (17b) (0.15 g,

0.43 mmol) in toluene (5 mL) and the mixture was

stirred for 5 min at room temperature. To this solu-

tion was added dropwise [Zr{Et(H)Si(g⁵-C₅H₄)₂}Cl₂]

(16b) (0.15 g, 0.31 mmol) in toluene (10 mL) and the

reaction mixture was stirred for 40 h at 100 ꢁC and

then allowed to cool to room temperature. The mix-

ture was ﬁltered and volatiles were removed from

the ﬁltrate under reduced pressure to give the title

product as a dark yellow oil (0.19 g, 92%). IR

0.37 mmol). Yield: 0.20 g, 99%. IR (KBr): m_CH3050,

1

m_CH@CH1591 cm^ꢀ1. H NMR (400 MHz, CDCl₃) (for

2

the major isomer): d 1.30 (3H), 1.40 (2H) (m, SiEt),

0.96 (2H), 1.23 (1H), 1.33 (1H) (m, CH₂CH₂), 1.93

(3H), 1.96 (3H), 2.05 (3H), 2.06 (3H) (s, C₅Me₄), 5.66

(1H), 5.70 (1H), 7.01 (2H) (m, C₅H₄), 5.85 (m, 3H,

CH₂@CH), 6.18 (m, 6H, CH₂@CH). ¹³C{¹H} NMR

(100 MHz, CDCl₃) (for the major isomer): d 4.0, 4.6

(SiEt), 4.4, 6.9 (CH₂CH₂), 12.4, 15.1, 15.2 (C₅Me₄),

106.4 (C^ipso), 112.6, 112.9, 126.6, 127.0 (C₅H₄), 98.0,

125.8, 126.2, 135.9, 136.1 (C₅Me₄), 133.6, 135.2

(CH@CH₂). ²⁹Si{¹H} NMR (79.49 MHz, CDCl₃) (for

(KBr): m_CH3046, m_CH¼CH1599 cm^ꢀ1

.

¹H NMR

2

(400 MHz, CDCl₃) (for the major isomer): d 1.31

(3H), 1.43 (2H) (m, SiEt), 0.95 (2H), 1.28 (2H) (m,

CH₂CH₂), 5.96 (2H), 6.00 (2H), 6.98 (4H) (m,

C₅H₄), 5.86 (m, 3H, CH₂@CH), 6.19 (m, 6H,

CH₂@CH). ¹³C{¹H} NMR (100 MHz, CDCl₃) (for

the major isomer):

(SiC₅H₄). MS electron impact (m/e (relative intensity)):

d

ꢀ18.2 (SiCH@CH₂), ꢀ8.7

the major isomer):

d 1.5, 7.5 (SiEt), 2.9, 4.3

538 (25) [M⁺], 503 (8) [M⁺ꢀ Cl], 109 (100)

(CH₂CH₂), 108.3 (C^ipso), 114.3, 115.0, 133.2, 136.0

(C₅H₄), 133.5, 135.3 (CH@CH₂). ²⁹Si{¹H} NMR

(79.49 MHz, CDCl₃) (for the major isomer): d ꢀ18.2

(SiCH@CH₂), ꢀ10.7 (SiC₅H₄). MS electron impact

(m/e (relative intensity)): 484 (15) [M⁺], 447 (7)

[M⁺ꢀ Cl], 310 (40) [M⁺ꢀ Cl, ꢀCH₂CH₂Si(CH@

CH₂)₃], 109 (100) [M⁺ꢀZr{CH₂CH₂Si(Et)(C₅H₄)₂}-

Cl₂]. Anal. Calc. for C₂₀H₂₆Cl₂Si₂Zr: C, 49.56; H,

5.41. Found: C, 49.09; H, 5.36%.

[M⁺ꢀ Zr{CH₂CH₂Si(Et)(C₅Me₄)(C₅H₄)}Cl₂].

Anal.

Calc. for C₂₄H₃₄Cl₂Si₂Zr: C, 53.30; H, 6.34. Found: C,

53.10; H, 6.31%.

5.36. [Ti{(CH₂@CH)Me₂SiCH₂CH₂(Et)Si(g⁵-C₅Me₄)-

(g⁵-C₅H₄)}Cl₂] (24a)

From SiMe₂(CH@CH₂)₂(0.037 g, 0.41 mmol) and

[Ti{Et(H)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (17a) (0.15 g,

0.41 mmol). Yield: 0.18 g, 93%. IR (KBr): m_CH3050,

The preparation of 23–26 was carried out in an iden-

tical manner to 22b.

m_CH@CH1599 cm^ꢀ1

.

¹H NMR (400 MHz, CDCl₃)

2

5.34. [Ti{(CH₂@CH)₃SiCH₂CH₂(Et)Si(g⁵-C₅Me₄)-

(g⁵-C₅H₄)}Cl₂] (23a)

(for the major isomer): d 0.18 (s, 6H, SiMe₂), 1.30

(3H), 1.41 (2H) (m, SiEt), 0.82 (2H), 1.28 (1H), 1.38

(1H) (m, CH₂CH₂), 1.86 (3H), 1.88 (3H), 2.15 (3H),

2.16 (3H) (s, C₅Me₄), 5.56 (1H), 5.58 (1H), 7.18

(2H) (m, C₅H₄), 5.76 (m, 1H, CH₂@CH), 6.11 (m,

2H, CH₂@CH). ¹³C{¹H} NMR (100 MHz, CDCl₃)

(for the major isomer): d ꢀ3.8 (SiMe₂), 3.9, 4.4 (SiEt),

7.0, 7.1 (CH₂CH₂), 13.6, 13.7, 16.2, 16.3 (C₅Me₄),

104.0 (C^ipso), 116.1, 116.3, 132.8, 133.3 (C₅H₄), 98.6,

131.1, 131.7, 144.0, 144.2 (C₅Me₄), 132.5, 137.7

(CH@CH₂). ²⁹Si{¹H} NMR (79.49 MHz, CDCl₃)

(for the major isomer): d ꢀ7.9 (Si C₅H₄), ꢀ3.4

(SiCH@CH₂). MS electron impact (m/e (relative inten-

sity)): 472 (38) [M⁺], 436 (40) [M⁺ꢀ Cl], 85 (100)

[M⁺ꢀ Ti{CH₂CH₂Si(Et)(C₅Me₄)(C₅H₄)}Cl₂], 59 (87)

[M⁺ꢀ CH@CH₂, ꢀTi{CH₂CH₂Si(Et)(C₅Me₄)(C₅H₄)}-

Cl₂]. Anal. Calc. for C₂₂H₃₄Cl₂Si₂Ti: C, 55.81; H,

7.24. Found: C, 55.55; H, 7.14%.

From Si(CH@CH₂)₄(0.056 g, 0.41 mmol) and

[Ti{Et(H)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (17a) (0.15 g,

0.41 mmol). Yield: 0.20 g, 98%. IR (KBr): m_CH3050,

m_CH@CH1592 cm^ꢀ1

.

¹H NMR (400 MHz, CDCl₃)

2

(for the major isomer): d 1.31 (3H), 1.41 (2H) (m,

SiEt), 0.99 (2H), 1.25 (1H), 1.35 (1H) (m, CH₂CH₂),

1.84 (3H), 1.88 (3H), 2.14 (3H), 2.15 (3H) (s,

C₅Me₄), 5.55 (1H), 5.58 (1H), 7.18 (2H) (m, C₅H₄),

5.84 (m, 3H, CH₂@CH), 6.18 (m, 6H, CH₂@CH).

¹³C{¹H} NMR (100 MHz, CDCl₃) (for the major iso-

mer): d 4.0, 4.9 (SiEt), 4.3, 7.0 (CH₂CH₂), 13.6, 13.7,

16.2, 16.3 (C₅Me₄), 103.8 (C^ipso), 116.0, 116.3, 132.8,

133.5 (C₅H₄), 98.5, 131.1, 131.7, 144.0, 144.3

(C₅Me₄), 133.3, 135.3 (CH@CH₂). ²⁹Si{¹H} NMR

(79.49 MHz, CDCl₃) (for the major isomer): d ꢀ18.2

´

S. Gomez-Ruiz et al. / Polyhedron 24 (2005) 1298–1313

1311

5.37. [Zr{(CH₂@CH)Me₂SiCH₂CH₂(Et)Si-

(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (24b)

6H, SiMe₂), 0.54 (q, 6H, SiCH₂CH₃), 0.96 (t, 9H,

SiCH₂CH₃), 1.27 (3H), 1.40 (2H) (m, CpSiEt), 0.4–1.1

(m, 8H, SiCH₂CH₂Si), 1.96 (3H), 1.97 (3H), 2.06 (6H)

(s, C₅Me₄), 5.67 (1H), 5.70 (1H), 7.02 (2H) (m, C₅H₄).

¹³C{¹H} NMR (100 MHz, CDCl₃) (for the major iso-

mer): d ꢀ4.3 (SiMe₂), 4.0,4.6 (CpSiEt), 3.0, 7.6 (SiEt₃),

3.3, 6.1, 6.8, 6.9 (CH₂CH₂), 12.3, 12.4, 15.0, 15.1

(C₅Me₄), 106.7 (C^ipso), 112.6, 112.9, 126.5, 126.0

(C₅H₄), 98.3, 125.6, 126.3, 135.9, 136.1 (C₅Me₄).

²⁹Si{¹H} NMR (79.49 MHz, CDCl₃) (for the major iso-

mer): d ꢀ9.0 (SiC₅H₄), 6.3 (SiCH₂CH₂), 8.2 (SiEt₃). MS

electron impact (m/e (relative intensity)): 630 (1) [M⁺],

595 (2) [M⁺ꢀ Cl], 515 (2) [M⁺ꢀ Et₃Si], 481 (4)

[M⁺ꢀ Cl, ꢀEt₃Si], 115 (74) [SiEt₃⁺], 93 (100)

[M⁺ꢀ Zr(C₅Me₄)Cl₂, ꢀCH₂CH₂SiMe₂(CH₂CH₂SiEt₃),

ꢀEt]. Anal. Calc. for C₂₈H₅₀Cl₂Si₃Zr: C, 53.12; H,

7.96. Found: C, 53.44; H, 8.08%.

From SiMe₂(CH@CH₂)₂(0.042 g, 0.37 mmol) and

[Zr{Et(H)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (17b) (0.15 g,

0.37 mmol). Yield: 0.19 g, 98%. IR (KBr): m_CH3047,

1

m_CH@CH1591 cm^ꢀ1. H NMR (400 MHz, CDCl₃) (for

2

the major isomer): d 0.18 (s, 6H, SiMe₂), 1.30 (3H),

1.41 (2H) (m, SiEt), 0.80 (2H), 1.22 (1H), 1.31 (1H)

(m, CH₂CH₂), 1.94 (3H), 1.97 (3H), 2.06 (6H) (s,

C₅Me₄), 5.67 (1H), 5.71 (1H), 7.02 (2H) (m, C₅H₄),

5.75 (m, 1H, CH₂@CH), 6.13 (m, 2H, CH₂@CH).

¹³C{¹H} NMR (100 MHz, CDCl₃) (for the major iso-

mer): d ꢀ3.8 (SiMe₂), 4.1, 4.5 (SiEt), 6.9, 7.0 (CH₂CH₂),

12.4, 12.5, 15.0, 15.1 (C₅Me₄), 106.0 (C^ipso), 112.6, 112.9,

126.5, 127.0 (C₅H₄), 98.2, 125.7, 126.3, 135.9, 136.1

(C₅Me₄), 132.4, 137.8 (CH@CH₂). ²⁹Si{¹H} NMR

(79.49 MHz, CDCl₃) (for the major isomer): d ꢀ8.8

(SiC₅H₄), ꢀ3.5 (SiCH@CH₂). MS electron impact (m/e

(relative intensity)): 516 (17) [M⁺], 478 (5) [M⁺ꢀ Cl],

85 (100) [M⁺ꢀ Zr{CH₂CH₂Si(Et)(C₅Me₄)(C₅H₄)}Cl₂],

59 (89) [M⁺ꢀ CH@CH₂, ꢀZr{CH₂CH₂Si(Et)(C₅Me₄)-

(C₅H₄)}Cl₂]. Anal. Calc. for C₂₂H₃₄Cl₂Si₂Zr: C, 51.13;

H, 6.63. Found: C, 51.09; H, 6.61%.

5.40. Synthesis of [Ti{Cl₂MeSiCH₂CH₂(Me)Si-

(g⁵-C₅Me₄)₂}Cl₂] (29a)

Two drops of the Karstedt catalyst (divin-

yltetramethylsiloxane Pt(0) in xylene (3–3.5%)) were

added to

a

solution of [Ti{CH₂@CH(Me)Si(g⁵-

C₅Me₄)₂}Cl₂] (0.30 g, 0.70 mmol) in toluene (10 mL)

and the mixture was stirred for 10 min at room temper-

ature. To this solution was added dropwise HSiMeCl₂

(0.08 g, 0.70 mmol) and the reaction mixture was stirred

for 2 h. The mixture was ﬁltered and volatiles removed

from the ﬁltrate under reduced pressure to give the title

product as a red crystalline solid (0.37 g, 97%). ¹H NMR

(400 MHz, CDCl₃) (for the major isomer): d 0.43 (s, 3H,

CpSiMe), 0.55 (s, 3H, Cl₂SiMe), 1.00 (2H), 1.31 (2H)

(m, CH₂CH₂), 1.64 (6H), 1.65 (6H), 2.06 (6H), 2.09

(6H) (s, C₅Me₄). ¹³C{¹H} NMR (100 MHz, CDCl₃)

(for the major isomer): d 0.0 (CpSiMe), 2.4 (Cl₂SiMe),

4.4, 9.5 (CH₂CH₂), 14.1, 14.2, 16.3, 16.5 (C₅Me₄),

92.1, 128.5, 128.7, 143.2, 143.4 (C₅Me₄). ²⁹Si{¹H}

NMR (79.49 MHz, CDCl₃) (for the major isomer): d

ꢀ9.5 (CpSiMe), 33.0 (Cl₂SiMe). MS electron impact

(m/e (relative intensity)): 546 (11) [M⁺], 508 (23)

[M⁺ꢀ Cl], 493 (100) [M⁺ꢀ Cl, ꢀMe], 349 (13)

[M⁺ꢀ CH₂CH₂SiMeCl₂, ꢀCl, ꢀMe], 321 (22) [M⁺ꢀ

CH₂CH₂SiMeCl₂, ꢀCl, ꢀ3 · Me], 286 (22) [M⁺ꢀ

CH₂CH₂SiMeCl₂, ꢀ2 · Cl, ꢀ3 · Me]. Anal. Calc. for

C₂₂H₃₄Cl₄Si₂Ti: C, 48.54; H, 6.30. Found: C, 48.33; H,

6.28%.

5.38. [Zr{(Et₃SiCH₂CH₂)₃SiCH₂CH₂(Et)Si-

(g⁵-C₅-Me₄)(g⁵-C₅H₄)}Cl₂] (25b)

From HSiEt₃(0.098 g, 0.84 mmol) and [Zr{(CH₂@

CH)₃SiCH₂CH₂(Et)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (23b)

(0.15 g, 0.28 mmol). Yield: 0.24 g, 97%. ¹H NMR

(400 MHz, CDCl₃) (for the major isomer): d 0.55 (q,

18H, SiCH₂CH₃), 0.97 (t, 27H, SiCH₂CH₃), 1.28 (3H),

1.42 (2H) (m, CpSiEt), 0.4–1.4 (m, 16H, SiCH₂CH₂Si),

1.97 (3H), 1.98 (3H), 2.07 (6H) (s, C₅Me₄), 5.66 (1H),

5.72 (1H), 7.02 (2H) (m, C₅H₄). ¹³C{¹H} NMR

(100 MHz, CDCl₃) (for the major isomer): d 3.6, 4.9

(CpSiEt), 3.0, 7.7 (SiEt₃), 2.9, 3.3, 3.6, 6.9 (CH₂CH₂),

12.4, 15.0, 15.1 (C₅Me₄), 106.6 (C^ipso), 112.5, 113.0,

125.5, 126.2 (C₅H₄), 98.3, 125.6, 127.0, 135.8, 136.2

(C₅Me₄). ²⁹Si{¹H} NMR (79.49 MHz, CDCl₃) (for the

major isomer): d ꢀ9.1 (SiC₅H₄), 8.1 (SiEt₃), 9.6

(SiCH₂CH₂). MS chemical ionization with CH₄(m/e

(relative intensity)): 886 (1) [M⁺], 121 (34) [M⁺ꢀ

Zr{Et₃Si(CH₂CH₂)₃SiCH₂CH₂(Et)Si(C₅H₄)}Cl₂], 115

(100) [SiEt₃⁺], 87 (33) [SiEt₂⁺]. Anal. Calc. for

C₄₂H₈₂Cl₂Si₅Zr: C, 56.70; H, 9.29. Found: C, 56.66;

H, 9.30%.

The preparation of 29b and 30 was carried out in an

identical manner to 29a.

5.39. [Zr{(Et₃SiCH₂CH₂)Me₂SiCH₂CH₂(Et)Si-

(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (26b)

5.41. [Zr{Cl₂MeSiCH₂CH₂(Me)Si(g⁵-C₅Me₄)₂}Cl₂]

(29b)

From HSiEt₃(0.034 g, 0.29 mmol) and [Zr{(CH₂@

CH)Me₂SiCH₂CH₂(Et)Si(g⁵-C₅Me₄)(g⁵-C₅H₄)}Cl₂] (24b)

(0.15 g, 0.29 mmol). Yield: 0.17 g, 91%. ¹H NMR

(400 MHz, CDCl₃) (for the major isomer): d 0.07 (s,

From HSiMeCl₂(0.11 g, 0.10 mmol) and [Zr{CH₂@

CH(Me)Si(g⁵-C₅Me₄)₂}Cl₂] (0.45 g, 0.10 mmol). Yield:

0.55 g, 96%. ¹H NMR (400 MHz, CDCl₃) (for the major

´

S. Gomez-Ruiz et al. / Polyhedron 24 (2005) 1298–1313

1312

isomer): d 0.42 (s, 3H, CpSiMe), 0.55 (s, 3H, Cl₂SiMe),

0.99 (2H), 1.32 (2H) (m, CH₂CH₂), 1.75 (6H), 1.76 (6H),

1.99 (6H), 2.02 (6H) (s, C₅Me₄). ¹³C{¹H} NMR

(100 MHz, CDCl₃) (for the major isomer): d 0.1

(CpSiMe), 0.5 (Cl₂SiMe), 4.6, 10.0 (CH₂CH₂), 13.0,

13.1, 15.5, 15.6 (C₅Me₄), 93.0, 124.5, 125.2, 136.1,

136.2 (C₅Me₄). ²⁹Si{¹H} NMR (79.49 MHz, CDCl₃)

(for the major isomer): d ꢀ11.0 (CpSiMe), 33.1

(Cl₂SiMe). MS electron impact (m/e (relative intensity)):

586 (35) [M⁺], 549 (12) [M⁺ꢀ Cl], 535 (23) [M⁺ꢀ Cl,

ꢀMe], 445 (15) [M⁺ꢀ CH₂CH₂SiMeCl₂], 304 (100)

[M⁺ꢀ Zr(C₅Me₄)Cl₂], 280 (40) [M⁺ꢀ C₅Me₄Si(Me)-

CH₂CH₂SiMeCl₂]. Anal. Calc. for C₂₂H₃₄Cl₄Si₂Zr: C,

44.96; H, 5.83. Found: C, 44.58; H, 5.76%.

using x/2h scan-technique. Absorption corrections were

applied using the ^SADABSprogram (maximum and mini-

mum transmission coeﬃcients 0.9608 and 0.7384). The

structure was solved using the Bruker SHELXTL-PC

software by direct methods and reﬁned by full-matrix

least-squares methods on F². All non-hydrogen atoms

were reﬁned anisotropically. Hydrogen atoms were in-

cluded in calculated positions (except H(1) which was lo-

cated in a diﬀerence map), and reﬁned in the riding

mode. Weights were optimized in the ﬁnal cycles. Crys-

tallographic data are given in Table 4.

5.45. X-ray structure determination of [Hf{CH₂@CH-

CH₂(H)Si(g⁵-C₅Me₄)₂}Cl₂] (21c)

5.42. [Zr{Cl₂MeSiCH₂CH₂CH₂(Me)Si(g⁵-C₅Me₄)₂}-

Cl₂] (30b)

Data were collected on a Bruker SMART CCD-

based diﬀractometer operating at 50 kV and 100 mA,

using x/2h scan-technique. The structure was solved

using the ^SHELXS-97 software by direct methods and re-

ﬁned by full-matrix least-squares methods on F². All

non-hydrogen atoms were reﬁned anisotropically.

Hydrogen atoms were included in calculated positions,

and reﬁned in the riding mode. Weights were optimized

in the ﬁnal cycles. Crystallographic data are given in

Table 4.

From HSiMeCl₂(0.12 g, 0.11 mmol) and [Zr{CH₂@

CHCH₂(Me)Si(g⁵-C₅Me₄)₂}Cl₂] (0.52 g, 0.11 mmol).

Yield: 0.61 g, 92%. H NMR (400 MHz, CDCl₃) (for

1

the major isomer): d 0.38 (s, 3H, CpSiMe), 0.67 (s,

3H, Cl₂SiMe), 0.91 (2H), 0.93 (2H), 1.27 (2H) (m,

CH₂CH₂CH₂), 1.75 (6H), 1.82 (6H), 2.00 (6H), 2.01

(6H) (s, C₅Me₄). ¹³C{¹H} NMR (100 MHz, CDCl₃)

(for the major isomer): d 0.2 (CpSiMe), 2.2 (Cl₂SiMe),

17.2, 22.2, 25.9 (CH₂CH₂CH₂), 13.0, 13.1, 15.6, 15.7

(C₅Me₄), 93.0, 124.5, 125.3, 136.1, 136.2 (C₅Me₄).

²⁹Si{¹H} NMR (79.49 MHz, CDCl₃) (for the major iso-

mer): d ꢀ13.5 (CpSiMe), 31.5 (Cl₂SiMe). MS electron

impact (m/e (relative intensity)): 598 (100) [M⁺], 564

(14) [M⁺ꢀ Cl], 549 (24) [M⁺ꢀ Cl, ꢀMe], 486 (13)

[M⁺ꢀ SiMeCl₂], 445 (23) [M⁺ꢀ CH₂CH₂CH₂SiMe-

Cl₂]. Anal. Calc. for C₂₃H₃₆Cl₄Si₂Zr: C, 45.91; H, 6.03.

Found: C, 45.44; H, 6.00%.

Table 4

Crystal data and structure reﬁnement for 21b and 21c

21b

21c

Formula

Formula weight

T (K)

C₂₁H₃₀Cl₂SiZr

472.66

298(2)

C_24.5H₃₄Cl₂HfSi

606.022

100(2)

Crystal system

Space group

monoclinic

C2/c

30.62(3)

monoclinic

P2(1)/c

˚

a (A)

18.43380(10)

10.01510(10)

26.2604(2)

91.9560(10)

4845.27(7)

8

5.43. Polymerization of ethylene

˚

b (A)

8.851(10)

17.175(18)

110.58(7)

4357(8)

˚

c (A)

The zirconocene catalyst (6 lmol), MAO (10% in tol-

uene) (1800 lmol) and toluene (200 mL) were mixed to-

gether for 15 min in a 1 L glass autoclave. The N₂

pressure inside the autoclave was reduced by applying

a vacuum. Ethylene pressure of 2 bar was then applied

and maintained to the autoclave and stirring of the mix-

ture commenced (1000 rpm). After exactly 15 min, stir-

ring was halted and the ethylene pressure released.

Excess MAO was then destroyed by adding cautiously

a mixture of methanol/HCl (90:10). The polymer was

isolated by ﬁltration and washed with ethanol and dried

under vacuum at 90 ꢁC for 16 h.

b (ꢁ)

3

˚

V (A )

Z

8

1.441

D_c(g cm^ꢀ3

)

1.650

10.513

2376

l (mm^ꢀ1

F(000)

)

0.807

1952

Crystal dimensions (mm)

h range (ꢁ)

hkl ranges

0.40 · 0.15 · 0.05

2.41 to 25.92

ꢀ37 6 h 6 36,

ꢀ9 6 k 6 10,

ꢀ14 6 l 6 21

4177/256

0.987

0.25 · 0.20 · 0.12

2.40 to 70.48

ꢀ19 6 h 6 22,

ꢀ10 6 k 6 11,

ꢀ30 6 l 6 30

8816/495

Data/parameters

Goodness-of-ﬁt on F²

Final R indices [I > 2r(I)]

1.026

R₁= 0.0465,

wR₂= 0.1026

R₁= 0.0905,

wR₂= 0.1182

0.507/ꢀ0.375

R₁= 0.0509,

wR₂= 0.1146

R₁= 0.0543,

wR₂= 0.1171

5.825/ꢀ4.816

R indices (all data)

5.44. X-ray structure determination of [Zr{CH₂@CH-

CH₂(H)Si(g⁵-C₅Me₄)₂}Cl₂] (21b)

Largest diﬀerence peak

ꢀ3

˚

and hole (e A

)

P

Data were collected on a Bruker SMART CCD-

based diﬀractometer operating at 50 kV and 30 mA,

R₁¼ jjF _oj ꢀ jF _cjj= jF _oj;

P

2

0.5

wR₂¼ f ½wðF ²_oꢀ F _c²Þ ꢁ= ½wðF ²_oÞ ꢁg

.

´

S. Gomez-Ruiz et al. / Polyhedron 24 (2005) 1298–1313

1313

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Crystallographic data for the structural analyses of 21b

and 21c have been deposited with the Cambridge Crystal-

lographic Data Centre, CCDC 261467 and 261468.

Copies of this information may be obtained free of charge

from The Director, CCDC, 12 Union Road, Cambridge

CB2 1EZ, UK (Fax: +44 1223 336 033; e-mail:

deposit@ccdc.cam.ac.uk or http//www.ccdc.cam.ac.uk).

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Acknowledgements

(e) C.J. Miller, D. OÕHare, Chem. Commun. (2004) 1710.

[6] (a) H.G. Alt, R. Ernst, I. Bo¨hmer, J. Mol. Catal. A 191 (2003)

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We gratefully acknowledge ﬁnancial support from

´

(b) H.G. Alt, R. Ernst, Inorg. Chim. Acta 350 (2003) 1;

(c) H.G. Alt, R. Ernst, J. Mol. Catal. A 195 (2003) 11.

[7] D. Seyferth, R. Wyrwa, US Pat. 5969073, 1999.

the Ministerio de Educacion y Ciencia, Spain (Grants

No. BQU2002-04638-C02-01 and MAT2003-05345),

the Junta de Comunidades de Castilla-La Mancha

(PAC-02-003 and PAI-02-010), the Comunidad de Ma-

drid (GR/MAT/0929/2004) and the Universidad Rey

Juan Carlos (GVC-2004-12). We also thank Repsol-

YPF for their assistance in the polymer analysis.

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Article Doi

Synthesis, hydrosilylation reactivity and catalytic properties of group 4 ansa-metallocene complexes

DOI: 10.1016/j.poly.2005.03.056

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