Catalytic and stoichiometric reactions of tertiary silanes with [Ir(Me)2Cp*L] (Cp*=η5-C5Me5; L=PMe3, PMe2Ph, PMePh2, PPh3) in the presence of one-electron oxidants. A unique case of SiH, SiC, IrC and PF bonds one-step activation: crystal structure of

The iridium(III) dimethyl derivatives [Ir(Me)2Cp*L] (Cp*=η5-C5Me5; L=PMe31a, PPh31d) catalyze the dehydrogenative coupling of dimethylphenylsilane in the presence of one-electron oxidants to yield Me2PhSiSiPhMe2. Compounds 1a–d react with triphenylsilane in the presence of [FeCp2]PF6 to give methane and [Ir(Ph)(SiFPh2)Cp*L] (L=PMe3 (2a), PMe2Ph (2b), PMePh2 (2c), PPh3 (2d)). 2a was structurally characterized by single-crystal X-ray diffraction experiments. The ‘three-legged piano stool’ coordination polyhedron is slightly deformed.