THE NATURE OF MU(3)-OXOHEXAKIS(MU-ACETATO)TRIAQUATRIRUTHENIUM CATIONIC COMPLEXES ISOLATED FROM AQUEOUS PERCHLORIC-ACID - CRYSTAL AND MOLECULAR-STRUCTURE OF [RU3O(O2CCH3)(6)(OH2)(3)](CLO4)CENTER-DOT-2H(2)O

Evaporation of 2.0 M HClO4 eluates following cation-exchange chromatog raphy of aqueous solutions of [Ru3O(O2CCH3)(6)(OH2)(3)](O2CCH3) has al lowed crystallisation and structural characterisation of the complex [ Ru3O(O2CCH3)(6)(OH2)(3)](ClO4).2H(2)O. A blue-green to purple colour c hange occurs in the mother liquor during the crystallisation process i ndicative of accompanying oxidation in solution to the purple dication ic Ru(III,III,IV) complex. Elution with more dilute (0.2 M) HClO4 solu tions allows only isolation of the Rn(III,III,IV) complex due to a hig her solubility and resulting oxidation by ClO4- ions prior to crystall isation. The structural analysis of [Ru3O(O2CCH3)(6)(OH2)(3)](ClO4).2H (2)O provides further support for the nonbonded character of the orbit als involved with electron transfer between the Ru(lII,III,III) and Ru (III,III,IV) forms of these complexes. Individual Ru-Ru and Ru-O dista nces indicate that in the Ru(III,III,IV) complex the Ru centres are va lence delocalised at room temperature.