The hydrosilylation of terminal alkynes is catalyzed by [Cp*IrCl2]2 to afford selectively the β-(Z)-vinylsilanes in high yields. A catalytic cycle based on an Ir(III)−Ir(V) redox process is proposed.

Reaction of the dimeric species [Cp*IrCl2]2 with a number of organic substrates carrying a terminal alkyne functionality (RCCH) in the presence of water leads to C⋮C bond cleavage to form Cp*IrCl(CH2R)(CO). The reaction pathway has been studied both experimentally and computationally.