Formation of Chlorosilyl Pincer-Type Rhodium Complexes by Multiple Si–H Activations of Bis(phosphine)/Dihydrosilyl Ligands

The synthesis and metalation of two bis­(phosphine)/dihydrosilyl ligands at rhodium­(I) sources is reported. Irrespective of the substitution at silicon (diaryl versus diamino), multiple Si–H activations and chloride migration afford tridentate bis­(phosphine)/chlorosilyl complexes of Rh­(I). For the diarylsilyl ligand, reaction with a cationic rhodium­(I) triflate precursor gives the analogous triflatosilyl complex. The [P2Si]­H2 proligands and their Rh complexes provide distinct opportunities for exploring metal/silicon cooperative reactivity.