Synthesis and Characterization of Ir-(κ²-NSi) Species Active toward the Solventless Hydrolysis of HSiMe(OSiMe₃)₂

The reaction of [IrH(Cl)(κ²-NSi^tBu2)(coe)] (1) with 1 equiv of PCy₃ (or PH^tBu₂) gives the species [IrH(Cl)(κ²-NSi^tBu2)(L)] (L = PCy₃, 2a; PH^tBu₂, 2b), which reacts with 1 equiv of AgOTf to afford [IrH(OTf)(κ²-NSi^tBu2)(L)] (L = PCy₃, 3a and PH^tBu₂, 3b). Complexes 2a, 2b, 3a, and 3b have been characterized by means of NMR spectroscopy and HR-MS. The solid-state structures of complexes 2a, 2b, and 3a have been determined by X-ray diffraction studies. The reversible coordination of water to 3a, 3b, and 4 to afford the corresponding adduct [IrH(OTf)(κ²-NSi^tBu2)(L)(H₂O)] (L = PCy₃, 3a-H₂O; PH^tBu₂, 3b-H₂O; coe, 4-H₂O) has been demonstrated spectroscopically by NMR studies. The structure of complexes 3b-H₂O and 4-H₂O have been determined by X-ray diffraction studies. Computational analyses of the interaction between neutral [NSi^tBu2]^• and [Ir(H)L(X)]^• fragments in Ir-NSi^tBu2 species confirm the electron-sharing nature of the Ir-Si bond and the significant role of electrostatics in the interaction between the transition metal fragment and the κ²-NSi ligand. The activity of Ir-(κ²-NSi^tBu2) species as catalysts for the hydrolysis of HSiMe(OSiMe₃)₂ depends on the nature of the ancillary ligands. Thus, while the triflate derivatives are active, the related chloride species show no activity. The best catalytic performance has been obtained when using complexes 3a, with triflate and PCy₃ ligands, as a catalyst precursor, which allows the selective obtention of the corresponding silanol.