Bridged pincer homodinuclear rare-earth metal complex-catalyzed hydrosilylation of 1-arylsubstituted and 1,1-disubstituted methylenecyclopropanes with diverse secondary silanes

Abstract

Catalytic hydrosilylation of 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 owing to the lack of an active catalyst. In this study, bridged pincer homodinuclear rare-earth metal complexes were found to be catalysts that 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 products, namely homoallylsilanes. While the hydrosilylation of 1-aryl methylenecyclopropanes (MCPs) bearing electron-withdrawing groups on the aryl moiety with primary and secondary silanes can generate the homoallylsilane products under controlled conditions, the selectivity is different from that of previously reported ones. Notably, it is found that the catalyst works well for the bis-hydrosilylation of different 1,1-diaryl MCPs with various primary silanes to deliver the ring-opening products.