Bridged Pincer Homodinuclear Rare-Earth Metal Complexes Catalyzed Hydrosilylation of 1-Arylsubstituted and 1,1-Disubstituted Methylenecyclopropanes with Diverse Secondary Silanes

Abstract

Catalytic hydrosilylation of the substituted methylenecyclopropanes is an important method for the preparation of homoallylsilanes and silacyclopentanes. However, the hydrosilylation of 1,1-disubstituted methylenecyclopropanes with secondary silanes is less developed for the lack of active catalyst. In this study, the bridged pincer homodinuclear rare-earth metal complexes were for the first time found as catalysts to enable the hydrosilylation of 1,1-diaryl MCPs with diverse secondary silanes like Ar₂SiH₂, homoallylsilanes and (aryl)(vinyl)silanes efficiently affording various ring-opening hydrosilylation product homoallylsilanes. While the hydrosilylation of 1-aryl methylenecyclopropanes (MCPs) bearing electron-withdrawing groups on aryl with primary and secondary silanes can generate the homoallylsilane products under controlled conditions, the selectivity is different from previous reported one. Notably, it is for the first time found that the catalyst works well for the bis-hydrosilylation of different 1,1-diaryl MCPs with various primary silanes to deliver the ringopening products.