Darstellung, Reaktivität und Kristallstruktur von [(CO)3Mn(dppm)2(μ-S)Rh(CO)] / Synthesis, Reactivity and Crystal Structure of [(CO)3Mn(dppm)2(μ-S)Rh(CO)

Abstract

The reaction of [(CO)3Mn(dppm)2Rh(CO)] (1) with H2S in dichloromethane yields [(CO)3Mn(dppm)2(μ-S)Rh(CO)] (2), which is characterized by IR, 31P{1H}, 1H, 13C{1H} nmr and mass spectra. The crystal structure of 2 was determined by X-ray diffraction: space group P21/n, Z = 4, a = 1232.6(3), b = 2558.8(4), c = 1640.8(2) pm, β = 97.74(2)°, R/Rw = 0.048/0.057. The dimeric complex shows A-frame structure possessing a bridging sulfur and a semibridging CO group. 2 cannot be oxidized to the corresponding SO2 bridged complex [(CO)3Mn(dppm)2(μ-SO2)Rh(CO)] (3). The reaction of 2 with SO2, however, yields the SO2 bridged complex [(CO)2Mn(dppm)2(μ-S)(μ-SO2)Rh(CO)] (5); in dichloromethane 2 is readily chlorinated to afford the salt [(CO)3Mn(dppm),(μ-S)RhCl]Cl (4).