SYNTHESIS, REACTIVITY AND CRYSTAL-STRUCTURE OF [(CO)3MN(DPPM)2(MU-S)RH(CO)]

The reaction of [(CO)3Mn(dppm)2Rh(CO)] (1) with H2S in dichloromethane yields [(CO)3Mn(dPPM)2(mu-S)Rh(CO)] (2), which is characterized by IR, P-31{H-1}, H-1, C-13{H-1} nmr and mass spectra. The crystal structure of 2 was determined by X-ray diffraction: space group P2(1)/n, Z = 4, a = 1232.6(3), b = 2558.8(4), c = 1640.8(2) pm, beta = 97.74(2)-degrees, R/R(w) = 0.048/0.057. The dimeric complex shows A-frame structure possessing a bridging sulfur and a semi-bridging CO group. 2 cannot be oxidized to the corresponding SO2 bridged complex [(CO)3Mn(dppm)2(mu-SO2)Rh(CO)] (3). The reaction of 2 with SO2, however, yields the SO2 bridged complex [(CO)2Mn(dppm)2(mu-S)(mu-SO2)Rh(CO)] (5); in dichloromethane 2 is readily chlorinated to afford the salt [(CO)3Mn(dppm)2(mu-S)RhCl]Cl (4).