In this work, the electronic structure and cyclo-addition reactivity of the first silylyne complex of a metal beyond group 6, [Cp*(iPr3P)(H)Os=Si(Trip)][HB(C6F5)3], were studied computationally. The computational NMR data on this novel compound and its cyclo-addition products matched experimental measurements perfectly, which supported the presence of a silylyne ligand. NBO and ETS-NOCV analysis revealed the nature of this Os�Si interaction as a triple bond consisting of a covalent s bond and two strong p back-donations. Kinetic control was found in the cyclo-addition reaction of the Os-Si triple bond by computational mechanistic studies and the origin of the kinetic control was rationalized by the energy decomposition analysis on the transition states and the cyclo-addition products (EDA). This work is a good demonstration on how to maximize the power of various computational tools in understanding the structures and reactivity of novel compounds.

Computational studies on structures and reactivity of an osmium silylyne complex

247th National Meeting (2014)

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