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Facile Interconversion of [Cp2(Cl)Hf(SnH3)] and [Cp2(Cl)Hf(μ-H)SnH2]: DFT Investigations of Hafnocene Stannyl Complexes as Masked Stannylenes
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Facile Interconversion of [Cp2(Cl)Hf(SnH3)] and [Cp2(Cl)Hf(μ-H)SnH2]: DFT Investigations of Hafnocene Stannyl Complexes as Masked Stannylenes

Julie Guihaume, Christophe Raynaud, Odile Eisenstein, Lionel Perrin, Laurent Maron and T. Don Tilley
Angewandte Chemie International Edition, Vol.49(10), pp.1816 - 1819
02/02/2010
DOI: https://doi.org/10.1002/anie.200906476

Abstract

DFT -stannylenes stannane dehydrocoupling hafnocene alpha-elimination
Sn two-step: Dehydrocoupling of stannanes by the d0 complex [Cp2(Cl)HfH] preferentially occurs by two successive reactions (see scheme): -bond metathesis to form [Cp2(Cl)Hf(SnH3)] and subsequent stannylene transfer into the Cp2(Cl)HfSnH3 bond. [Cp2(Cl)Hf(SnH3)] readily isomerizes to a species possessing a reactive stannylene unit, [Cp2(Cl)Hf(-H)SnH2], thus making the stannylene-transfer reaction energetically feasible.
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