Redox properties of rhodium(III) oxo-bridged carboxylate complexes

• Chemical and electrochemical oxidation of rhodium (III) oxo-bridged carboxylate complexes was studied. The chemical [with O-3 and Ce(IV) salts] or electrochemical (at potentials of 1.00-1.20 V) oxidations of the binuclear complexes [Rh-2(mu-O)(mu-O2CCH3)(2)(H2O)(6)](2+) and [Rh-2(mu-O)(mu-O2CCF3)(2)(H2O)(6)](2+) leads to the superoxo complexes [Rh-2(mu-O)(O-2(-))(mu-O2CCH3)(2)(H2O)(5)]+ and [Rh-2(mu-O)(O-2(-))(mu-O2CCF3)(2)(H2O)(5)](+) with terminal coordination of O-2(-). The trinuclcar acetate [Rh-3(mu(3)-O)(mu-O2CCH3)(6)(H2O)(3)](+), unlike its trifluoroacetate analog [Rh-3(mu(3)-O)(mu-O2CCF3)(6)(H2O)(3)](+), is oxidized only electrochemically at a potential of 1.38 V. The oxidation of [Rh-3(mu(3)-O)(mu-O2CCH3)(6)(H2O)(3)](+) is reversible and involves formation of an unstable superoxo group O-2(-) between two Rh-3(III)(mu(3)-O) cores.

Nyckelord

electronic-structure

metal-complexes

trinuclear

crystal

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