Cubane‐Type [Mo3S4M] Clusters with First‐Row Groups 4–10 Transition‐Metal Halides Supported by C5Me5 Ligands on Molybdenum.

A synthetic protocol was developed for a series of cubane‐type [Mo3S4M] clusters that incorporate halides of first‐row transition metals (M) from Groups 4–10. This protocol is based on the anionic cluster platform [Cp*3Mo3S4]− ([1]−; Cp*=η5‐C5Me5), which crystallizes when K(18‐crown‐6) is used as the counter cation. Treatment of in situ‐generated [1]− with such transition‐metal halides led to the formation of [Mo3S4M] clusters, in which the M/halide ratio gradually changes from 1:2 to 1:1.5 and to 1:1, when moving from early to late transition metals. This trend suggests a tendency for early transition metals to tolerate higher oxidation states and adopt larger ionic radii relative to late transition metals. The properties of the [Mo3S4Fe] cluster 6 a were investigated in detail by using 57Fe Mössbauer spectroscopy and computational methods. Cubic clusters: A synthetic protocol was developed for a series of cubane‐type [Mo3S4M] clusters, based on the anionic cluster platform [Cp*3Mo3S4]−, which incorporate halides of first‐row transition metals (M) from Group 4–10. The M/halide ratio gradually increases from 1:2 to 1:1.5 and to 1:1 upon moving from early to late transition metals. [ABSTRACT FROM AUTHOR]