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Synthesis of [Mo 3 S 4 ] Clusters from Half-Sandwich Molybdenum(V) Chlorides and Their Application as Platforms for [Mo 3 S 4 Fe] Cubes.
Inorganic Chemistry 2019 March 23
Triangular [Mo3 S4 ] clusters are known to serve as platforms to accommodate a metal atom M, furnishing cubic [Mo3 S4 M] clusters. In this study, three [Mo3 S4 ] clusters supported by η5 -cyclopentadienyl (CpR ) ligands, [CpR 3 Mo3 S4 ]+ (CpR = C5 Me4 SiMe3 , C5 Me4 SiEt3 , and C5 Me4 H), were synthesized via half-sandwich molybdenum chlorides CpR MoCl4 . In the cyclic voltammogram of the [Mo3 S4 ] cluster having C5 Me4 H ligands, a weak feature appeared in addition to the [CpR 3 Mo3 S4 ]0/- redox process, indicating the interaction between [CpR 3 Mo3 S4 ]- and the [Nn Bu4 ] cation of the electrolyte, while such a feature was less significant for the C5 Me4 SiR3 variants. The [Mo3 S4 ] clusters with bulky C5 Me4 SiR3 ligands were successfully applied as platforms to accommodate an Fe atom to furnish cubic [Mo3 S4 Fe] clusters. On the other hand, the corresponding reactions of the less bulky C5 Me4 H analogue gave complex mixtures.
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