The complex [Rh(ItBu)2HCl] has been shown to be an active catalyst in the hydrosilylation of carbonyl and imine complexes. This reactivity, combined with the previously reported H/D exchange catalyzed by these complexes allows for a one pot, two step reaction using a single catalyst for both H/D exchange and hydrosilylation. Using triethylsilane, [Rh(ItBu)2Cl] catalyst, and D2 gas, deuterated silyl-ethers can be synthesized in an atom-economical, solvent-free reaction.