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Redox properties of rhodium(III) oxo-bridged carboxylate complexes
- Belyaev, A. N. (author)
- Simanova, S. A. (author)
- Gorlov, Mikhail (author)
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- Bashmakov, V. I. (author)
- Panina, N. S. (author)
- Vyatkin, V. E. (author)
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- 2001
- 2001
- English.
- In: Russian journal of general chemistry. - 1070-3632 .- 1608-3350. ; 71:8, s. 1186-1193
- Journal article (peer-reviewed)
Abstract
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- 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.
Keyword
- electronic-structure
- metal-complexes
- trinuclear
- crystal
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- ref (subject category)
- art (subject category)
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- Belyaev, A. N.
- Simanova, S. A.
- Gorlov, Mikhail
- Bashmakov, V. I.
- Panina, N. S.
- Vyatkin, V. E.
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- Royal Institute of Technology
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