Si-H Bond [Seminar] Activation of Hydrosilanes with Perfluoroalkyl Rhodium Porphyrin Complexes, by Prof. Ching Tat To, Tunghai University

Title: Si-H Bond Activation of Hydrosilanes with Perfluoroalkyl Rhodium Porphyrin Complexes

Speaker: Dr Ching Tat To, Associate Professor, Department of Chemistry, Tunghai University, Taichung City, Taiwan

Abstract:
Activation of hydrosilanes by transition metal complexes is a cornerstone for the synthesis of functionalized organosilanes through Si-H bond cleavage. While this process typically proceeds via oxidative addition to form silyl metal species,1 our group has explored alternative pathways using perfluoroalkyl rhodium(III) porphyrin complexes, RhIII(ttp)RF.2
Our group demonstrate that these complexes effectively cleave Si-H bonds to generate silyl rhodium(III) species and hydrofluorocarbon (RFH) co-products. Mechanistic investigations reveal that the cleavage process is governed by the perfluoroalkyl ligand, following a dual pathway consisting of direct -bond metathesis and -F elimination. Our findings indicate that the silicon center acts as a nucleophile during the transition state, providing new insights into the reactivity of these perfluoroalkyl organometallic complexes.

References
1. (a) Corey, J. Y. Chem. Rev. 2016, 116, 11291-11435. (b) Corey, J. Y. Chem. Rev. 2011, 111, 863-1071.
2. Fu, L.-J.; An, B.-H.; Chou, C.-H.; Chen, C.-M.; To, C. T. Dalton Trans. 2021, 50, 9949-9957.