From Remote Alkenes to Linear Silanes or Allylsilanes depending on the Metal Center

Abstract The selective synthesis of linear silanes or allylsilanes from remote alkenes was explored. The cationic, unsaturated, 16‐electron hydrido–silyl–Rh III complex was found to be an efficient catalyst for a tandem catalytic alkene isomerization–hydrosilylation reaction at room temperature under solvent‐free conditions. The analogous hydrido–silyl–Ir III complex was selective for dehydrogenative silylation, which led to the formation of terminal allylsilanes.