[Me2C(C5H4)2TiMe2]:
An Open-Bent Titanocene Catalyst for the Hydro­silylation
of Bulky 1,3-Dienes

Roxana Pop; Jin Lan Cui; Louis Adriaenssens; Virginie Comte; Pierre Le Gendre

doi:10.1055/s-0030-1259687

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Synlett 2011(5): 679-683
DOI: 10.1055/s-0030-1259687

LETTER

[Me₂C(C₅H₄)₂TiMe₂]: An Open-Bent Titanocene Catalyst for the Hydrosilylation of Bulky 1,3-Dienes

Roxana Pop^a, Jin Lan Cui^b, Louis Adriaenssens^a, Virginie Comte^a, Pierre Le Gendre*^a
^a Institut de Chimie Moléculaire de l’Université de Bourgogne, ICMUB-UMR CNRS 5260, Université de Bourgogne, 9 Avenue Alain Savary, BP 47870, 21078 Dijon Cedex, France
e-Mail: pierre.le-gendre@u-bourgogne.fr;
^b Department of Chemistry, University of Louisville, 2320 South Brook Street, Louisville, KY 40292, USA

Further Information

Publication History

Received 30 November 2010
Publication Date:
25 February 2011 (online)

Abstract
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Abstract

Motivated by our preliminary results on Cp₂TiF₂-catalysed 1,4-hydrosilylation of monosubstituted dienes, we assessed the performance of several titanium complexes for the hydrosilylation of 2,3-dimethylbutadiene, a representative bulky diene. An open-bent titanocene complex [Me₂C(C₅H₄)₂TiMe₂] performed the best and proved to be efficient for the hydrosilylation of a variety of substrates such as disubstituted dienes, activated alkenes, and even an acetylene.

Key words

hydrosilylation - titanium - diene - allylsilane - homogeneous catalysis

References and Notes

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11

The efficacy of Cp₂TiF₂ in the hydrosilylation of mono-substituted 1,3-dienes prompted us to assess the catalytic performance of the difluoro-ansa-titanocene. Unfortunately, in our hands activation of the ansa-difluorotitanocene precatalyst was not possible.

12

The geometry of 2 was determined to be E by comparison of the NMR spectra with those reported previously, see ref. 5.

13

The E configuration of 5 and 6 was unambiguously determined by NOESY NMR experiments.