Complexes displaying multiple bonds between different metal atoms have considerable synthetic potential because of the combination of the high electronic and coordinative unsaturation associated to multiple bonds with the intrinsic polarity of heterometallic bonds but their number is scarce and its chemistry has been relatively little explored. In a preliminary study, our attempted synthesis of the unsaturated hydrides [MoMCp(μ-H)(μ-PR2)(CO)5] from anions [MoMCp(μ-PR2)(CO)5]− and (NH4)PF6 yielded instead the ammonia complexes [MoMCp(μ-H)(μ-PR2)(CO)5(NH3)] (M = Mn, R = Ph; M = Re, R = Cy). We have now examined the structure and behaviour of the MoMn complex (Mo–Mn = 3.087(3) Å) and found that it easily dissociates NH3 (this requiring some 40 kJ/mol, according to DFT calculations), to yield the undetectable unsaturated hydride [MoMnCp(μ-H)(μ-PPh2)(CO)5] (computed Mo–Mn = 2.796 Å), the latter readily adding simple donors L such as CNR (R = Xyl, p-C6H4OMe) and P(OMe)3, to give the corresponding electron-precise derivatives [MoMnCp(μ-H)(μ-PPh2)(CO)5(L)]. Thus the ammonia complex eventually behaves as a synthetic equivalent of the unsaturated hydride [MoMnCp(μ-H)(μ-PPh2)(CO)5]. The isocyanide derivatives retained the stereochemistry of the parent complex (Mo–Mn = 3.0770(4) Å when R = Xyl) but a carbonyl rearrangement takes place in the reaction with phosphite to leave the entering ligand trans to the PPh2 group, a position more favoured on steric grounds.