Mixed-valence, tetranuclear cobalt(iii,iv) complexes: preparation and properties of [Co4O4(O2CR)2(bpy)4 ]3+ salts
Abstract
Cyclic voltammetric examination of [Co4O4(O2CR)2- (bpy)4](ClO4)2 cubane complexes 1 (R = various; bpy = 2,2′-bipyridine) in MeCN reveals a one-electron reversible oxidation in the range 0.68–0.86 V vs. ferrocene; the one-electron oxidized clusters can be obtained in analytical purity by either controlled potential electrolysis to give [Co4O4(O2CR)2(bpy)4 ](ClO4)32 or oxidation with (NH4)2Ce(NO3)6 to give [Co4O4(O2CR)2(bpy)4 ][Ce(NO3)6] 3.