Catalytic and stoichiometric reactions of tertiary silanes with [Ir(Me) 2Cp*L] (Cp*=η 5-C 5Me 5; L=PMe 3, PMe 2Ph, PMePh 2, PPh 3) 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 [Ir(Ph)(SiPh 2F)Cp*(PMe 3)

Abstract

The iridium(III) dimethyl derivatives [Ir(Me) 2Cp*L] (Cp*=η 5-C 5Me 5; L=PMe 3 1a, PPh 3 1d) catalyze the dehydrogenative coupling of dimethylphenylsilane in the presence of one-electron oxidants to yield Me 2PhSiSiPhMe 2. Compounds 1a– d react with triphenylsilane in the presence of [FeCp 2]PF 6 to give methane and [Ir(Ph)(SiFPh 2)Cp*L] (L=PMe 3 ( 2a), PMe 2Ph ( 2b), PMePh 2 ( 2c), PPh 3 ( 2d)). 2a was structurally characterized by single-crystal X-ray diffraction experiments. The ‘three-legged piano stool’ coordination polyhedron is slightly deformed.