Redox Properties of Thiolate Compounds of Oxomolybdenum(V) and Their Tungsten and Selenium Analogues

Abstract

The rich electrochemistry of the mononuclear [MvO(XR)4]- and triply bridged binuclear [Mv202(XR)6Z]n- anions (M = Mo, W; X = S, Se; R = Ph, p-tolyl, CH2Ph; Z = uninegative (n = 1) or neutral (n = 0) ligand) is explored in MeCN and DMF at platinum and mercury electrodes over the temperature range +25 to -60 °C. Interconversion of the mononuclear and binuclear forms occurs via reduction and oxidation processes involving the metal and ligand centers. Stepwise reduction of the binuclear Mv2 to MIV,V2 and MIV *2 species is observed, and the reduced forms undergo chemical reactions which lead to the appearance of 1 molecule of [MrvO(XR)1 4]2-/molecule of [Mv2O2(XR)6Z]- reduced. In this way, the al..