Activation of Dichloromethane by (Phosphane)orhodium(I) Complexes − X-ray Structure of [{(PEt3)2RhCl}2(μ-Cl)2(μ-CH2)]

Dichloromethane reacts with dinuclear rhodium complexes [{(PR3)2Rh}2(μ-Cl)2] to give the bridging-methylene complexes [{(PR3)2RhCl}2(μ-Cl)2(μ-CH2)] (PR3 = PEt3, PPh2Me). The structure of the PEt3 complex has been established by X-ray diffraction study. The early stages of the reaction of [{(C8H14)2Rh}2(μ-Cl)2] with monophosphanes have been monitored by 31P NMR, evidencing chloride bridges cleavage and phosphane redistribution processes.