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Redox properties of rhodium(III) oxo-bridged carboxylate complexes
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2001 (English)In: Russian journal of general chemistry, ISSN 1070-3632, E-ISSN 1608-3350, Vol. 71, no 8, 1186-1193 p.Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
2001. Vol. 71, no 8, 1186-1193 p.
Keyword [en]
electronic-structure, metal-complexes, trinuclear, crystal
Identifiers
URN: urn:nbn:se:kth:diva-21279ISI: 000173525700006OAI: oai:DiVA.org:kth-21279DiVA: diva2:339977
Note
QC 20100525Available from: 2010-08-10 Created: 2010-08-10Bibliographically approved

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