The hydride-supported [Mo Fe ] cluster complex {Cp*Mo(PMe )} {FeN(SiMe ) } (H) (2 a; Cp*=η -C Me ) and its [Mo Mn ] congener 2 b were synthesized from the reactions of Cp*Mo(PMe )(H) (1) with M{N(SiMe ) } (M=Fe, Mn). The amide-to-thiolate ligand-exchange reactions of complex 2 a with bulky thiol reagents (HSR; R=2,4,6-iPr C H (Tip), 2,6-(SiMe ) C H (Btp)) furnished the corresponding hydride-supported [Mo Fe ](SR) cluster complexes. The [Mo Fe ] clusters served as catalyst precursors for the reductive silylation of N and yielded ≈65–69 equivalents of N(SiMe ) relative to the [Mo Fe ] clusters. Treatment of complexes 2 a and b with an excess of CNtBu resulted in the formation of dinuclear Mo−Fe and Mo−Mn complexes, which indicated that the [Mo M ] cores (M=Fe, Mn) split into two dinuclear species upon accommodation of substrates. 2 2 3 2 3 2 2 8 5 5 2 2 3 5 3 2 2 3 6 2 3 2 6 3 2 2 2 2 2 2 3 3 2 2 2 2 5