Metal catalysts for functionalization of C–H bonds in organic molecules are attracting considerable attention because this functionalization can be applied to development of straightforward methods for the synthesis of chemical products such as pharmaceutical compounds and functional materials. In our recent study, iridium complexes featuring silicon-based chelate ligands were found to catalyze unprecedented regio- and stereoselective C(sp3)–H deuteration of tricyclohexylphosphine under mild conditions (60℃). The silicon-based supporting ligands enhance efficiently the reactivity of the iridium center due to their strong electron-donating nature, which facilitates C–H oxidative addition.