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A Stable Silylene with a σ2, π- Butadiene Ligand
Zhaowen Dong1, Crispin R W Reinhold1, Marc Schmidtmann1
1Institute of Chemistry, Carl von Ossietzky University of Oldenburg , Carl von Ossietzky-Str. 9-11, D-26129 Oldenburg, Federal Republic of Germany, European Union.
Abstract:
The synthesis of a new type of silylene 1 is reported. It adopts a bicyclo[2.1.1]hexene structure in which a hafnocene group is incorporated. The silylene is stabilized by homoconjugation with the remote C═C double bond. This is indicated by its highly shielded 29Si NMR chemical shift (δ29Si = -155) and is firmly established by its experimental molecular structure from XRD analysis. The results of a detailed bonding analysis based on DFT calculations suggest for model compounds of silylene 1 and for its heavier germanium, tin, and lead homologues uniformly electronic structures of carbene analogues that are stabilized by homoconjugation. This stabilization mode is equivalent to a σ2, π-coordination of the butadiene ligand to the element atom as it is typical for zirconocene or hafnocene butadiene complexes.
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