• Stepwise reduction of electron-precise, six-electron, triangular, [Mo3IVS4(CN)9]5− to electron-rich seven, eight and unstable nine-electron species resulting in core expansion to electron-precise, twelvee-lectron, tetrahedral, [Mo4IIIS4(CN)12]8−to electron-rich seven, eight and unstable nine-electron species resulting in core expansion to electron-precise, twelvee-lectron, tetrahedral, [

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    • Keywords

       

      Trinuclear; tetranuclear; molybdenum-sulphur clusters; cluster core expansion

    • Abstract

       

      Facile reduction of the triangular {Mo3IV}6-core containing [Mo3S4 (CN)9]5− derivative is achieved in aqueous medium, containing the KOH-KCN-K2 [Zn(CN)4] ternary system as supporting electrolyte, in a two-step one-electron reduction reaction followed by an irreversible one. The diamagnetic species containing the {Mo3}8 core, obtained by chemical reduction of [Mo3S4(CN)9]5− with zinc in aqueous medium containing KOH-KCN, is oxidized by air in two steps. The partially oxidized species with {Mo3}7 core in the first step exhibits characteristic ESR signals which on further oxidation quantitatively reverts to the original compound with {Mo3}6 core displaying distinctly separate isosbestic points in the stepwise conversion of {Mo3}8 to {Mo3}7 and {Mo3}7 to {Mo3}6 cores. Under drastic reduction conditions with aluminium in 40% aqueous KOH solution the {Mo3}6 core is reduced to unstable trinuclear {Mo3III}9 core which expands to tetrahedral {Mo4III}12-core containing [Mo4S4(CN)12]8− derivative according to electron-precise cluster rule.

    • Author Affiliations

       

      Sabyasa Chisarkar1 Ramji Sah1 Pradeep K Chaudhury1 Rabindranath Maiti1 Samar K Das1

      1. Department of Chemistry, Indian Institute of Technology, Kanpur - 208016, India
    • Dates

       
  • Journal of Chemical Sciences | News

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