Redox Properties of Rhodium(III) Oxo-Bridged Carboxylate Complexes |
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| Authors: | Belyaev A. N. Simanova S. A. Gorlov M. Yu. Bashmakov V. I. Panina N. S. Vyatkin V. E. |
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| Affiliation: | (1) St. Petersburg State Institute of Technology, St. Petersburg, Russia;(2) Khlopin Radium Institute, St. Petersburg, Russia |
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| Abstract: | Chemical and electrochemical oxidation of rhodium (III) oxo-bridged carboxylate complexes was studied. The chemical [with O3 and Ce(IV) salts] or electrochemical (at potentials of 1.00-1.20 V) oxidations of the binuclear complexes [Rh2( -O)(-O2CCH3)2(H2O)6]2+ and [Rh2(-O)(-O2CCF3)2(H2O)6]2+ leads to the superoxo complexes [Rh2(-O)(O2-)(-O2CCH3)2(H2O)5]+ and [Rh2(-O)(O2-)(-O2CCF3)2(H2O)5]+ with  terminal coordination of O2-. The trinuclear acetate [Rh3(3-O)(-O2CCH3)6(H2O)3]+, unlike its trifluoroacetate analog [Rh3(3-O)(-O2CCF3)6(H2O)3]+, is oxidized only electrochemically at a potential of 1.38 V. The oxidation of [Rh3(3-O)(-O2CCH3)6(H2O)3]+ is reversible and involves formation of an unstable superoxo group O2- between two Rh3III(3-O) cores. |
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