Synthesis and Structural Characterization of Group 7 and 8 Metal-Thiolate Complexes

Thermolysis of [Cp*Ru(A mu-H)BH(L)(2)] (Cp* = eta(5)-C5Me5, L = C7H4NS2), (1) with [Mn-2(CO)(10)] led to the formation of a transmetallated complex [Mn(CO)(3)(A mu-H)BH(L)(2)], (2) and a ruthenium-thiolate complex [(Cp*RuCO)(2)(L)(2)], (3) in moderate yields. Compound 2 can also be generated from a direct reaction of [Mn-2(CO)(10)] and [NaBt] (Bt = dihydrobis(2-mercaptobenzthiazolyl)borate). Although all of our attempts to generate [M(CO)(3)(A mu-H)(2)BHL] (M = Mn or Re) from the bis(sigma-borate) complex [Cp*Ru(A mu-H)(2)BHL] (L = C7H4NS2), (4) were failed, thermolysis of 4 with [Mn-2(CO)(10)] yielded a sigma-borane complex [Cp*RuCO(A mu-H)BH2L], (5) and a mixed-metal thiolate complex [(Cp*RuCO)(2)(A mu(3)-S)Mn(CO)(3)L], (6). Further, the reaction of compound 5 with [Mn-2(CO)(10)] yielded heterocyclic thiolate complex [Cp*Ru(CO)(2)L)], (7). Thermolysis of 4 with [Re-2(CO)(10)] does not yield any products. However, under photolytic conditions it led to the formation of mixed-metal thiolate complex [(Cp*RuCO)Re(CO)(3)(L)(2)], (8). All the compounds have been characterized by mass spectrometry, IR, H-1, C-13 spectroscopy, and the X-ray structures of 2-3 and 5-8 were unequivocally established by crystallographic analysis.