Phosphino alkylsilanes in which Si is connected to P through a benzylic framework have been synthesized and used as precursors to chelate ligand systems which attach to transition metal centers through a silicon-metal bond supported by one, two, or three intramolecular phosphorus-metal bonds. The resulting stereochemistry around Ir(III) in IrH(mctriPSi)Cl (7), in which quadridentate coordination of the mctriPSi ligand cage leads to occupation of four adjacent octahedral sites with H trans to P and Cl trans to Si, is assigned using multinuclear NMR spectroscopy.