Thermolysis of [Cp*Ru(µ-H)BH(L)2] (Cp* = η5-C5Me5, L = C7H4NS2), (1) with [Mn2(CO)10] led to the formation of a transmetallated complex [Mn(CO)3(µ-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 [Mn2(CO)10] and [NaBt] (Bt = dihydrobis(2-mercaptobenzthiazolyl)borate). Although all of our attempts to generate [M(CO)3(µ-H)2BHL] (M = Mn or Re) from the bis(σ-borate) complex [Cp*Ru(µ-H)2BHL] (L = C7H4NS2), (4) were failed, thermolysis of 4 with [Mn2(CO)10] yielded a σ-borane complex [Cp*RuCO(µ-H)BH2L], (5) and a mixed-metal thiolate complex [(Cp*RuCO)2(µ3-S)Mn(CO)3L], (6). Further, the reaction of compound 5 with [Mn2(CO)10] yielded heterocyclic thiolate complex [Cp*Ru(CO)2L)], (7). Thermolysis of 4 with [Re2(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, 1H, 13C spectroscopy, and the X-ray structures of 2–3 and 5–8 were unequivocally established by crystallographic analysis. © 2016, The National Academy of Sciences, India.