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JOURNAL ARTICLE
RESEARCH SUPPORT, NON-U.S. GOV'T
A Stable Silylene with a σ 2 , π- Butadiene Ligand.
Journal of the American Chemical Society 2017 May 25
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 29 Si NMR chemical shift (δ29 Si = -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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