Hydrosilylation of alkynylsilanes utilizing organolanthanide and Group 3 metallocene complexes

The organolanthanide- and Group 3 metallocene-catalyzed hydrosilylation of alkynylsilanes has been found to provide (Z)-1,1-bis(silyl)alkenes. In particular, Cp*2YMe·THF (1), [CpTMS2YMe]2 (2), and [CpTMS2LuMe]2 (3) were shown to be regioselective for the hydrosilylation of various alkynylsilanes ( Fig. 1). The process was evaluated for diverse substitution patterns and functional groups on the pendant alkyl chain. Silyl ethers and halogens are stable to the catalytic process, affording excellent chemo- and regioselectivities. Competition between ‘aryl-directed’ and ‘silyl-directed’ processes was observed upon hydrosilylation of (phenylethynyl)dimethylsilane.