The complex [RhMn(CO)4(dppm)2] (dppm = Ph2PCH2PPh2) reacts with H2S and thiols to yield the products [RhMn(SR)(CO)3(mu-H)(dppm)2] (R = H, Et, Ph), containing terminal sulfhydryl or thiolato groups bound to Rh and a bridging hydride ligand. The sulfhydryl species loses H-2 over the period of several days and scavenges CO to yield [RhMn(CO)4(mu-S)(dppm)2]. This sulfide-bridged product can be protonated or alkylated to give the cationic species [RhMn(CO)4(mu-SR)(dppm)2]+ (R = H, CH3, CH2SiMe3), containing bridging sulfhydryl or thiolato groups. The bridging sulfhydryl group in [RhMn(CO)4(mu-SH)(dppm)2]+ Undergoes a Michael-type addition to alkynes to yield [RhMn(CO)4(mu-SC(R) = C(H)R’)(dppm)2]+ (R = H, R’= C(O)Me; R = R’= CO2Me) in which the unsaturated thiolato group bridges the metals. With hexafluoro-2-butyne, an analogous reaction occurs to yield the related species [RhMn(SC(CF3) = C(H)CF3)(CO)4(dppm)2]+, but in this case the thiolato group is terminally bound to Rh. The structure of [RhMn(CO)4(mu-S)(dppm)2] has been determined by X-ray crystallography. This compound crystallizes in the monoclinic space group P2(1)/n, with a = 12.419(4) angstrom, b = 25.735(2) angstrom, c = 16.464(2) angstrom, beta = 97.70(2)-degrees, V = 5215(3) angstrom, and Z = 4, and has refined to R = 0.055 and R(W) = 0.071 on the basis of 5865 unique observations and 598 parameters varied. This compound shows a semibridging carbonyl group which is primarily bound to Mn (Mn-C(2) = 1.959(5) angstrom, Rh-C(2) = 2.214(5) angstrom), in line with the small Rh-C coupling of 8 Hz observed in the C-13 NMR for this carbonyl.