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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
The osmium-silicon triple bond: synthesis, characterization, and reactivity of an osmium silylyne complex
Paul G Hayes1, Zhenggang Xu, Chad Beddie
1Department of Chemistry, University of California, Berkeley, Berkeley, California 94720-1460, USA.
Abstract:
The first silylyne complex of a metal beyond group 6, [Cp*((i)Pr3P)(H)Os≡Si(Trip)][HB(C6F5)3], was prepared by a new synthetic route involving hydride abstraction from silicon. NMR and DFT computations support the presence of a silylyne ligand, and NBO and ETS-NOCV analysis revealed the nature of this Os-Si interaction as a triple bond consisting of a covalent σ bond and two strong π back-donations. The discovery of this complex allowed observations of the first cycloadditions involving a silylyne complex, and terminal alkynes are shown to react via C-H bond additions across the Os≡Si bond.
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