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dc.contributor.authorGennett, Thomasen_US
dc.contributor.authorGeiger, Williamen_US
dc.contributor.authorWillet, Brianen_US
dc.contributor.authorAnson, Freden_US
dc.date.accessioned2006-07-19T19:34:25Zen_US
dc.date.available2006-07-19T19:34:25Zen_US
dc.date.issued1987-05-08en_US
dc.identifier.citationJournal of Electroanalytical Chemistry 222N1-2 (1987) 151-160en_US
dc.identifier.issn0022-0728en_US
dc.identifier.urihttp://hdl.handle.net/1850/2152en_US
dc.description.abstractHeterogeneous electron-transfer rates have been measured for three binuclear complexes, Cp2Fe2(CO)2(μ-SMe)2, 1, Cp2Fe2(CO)2(μ-PPh2)2, 2, and Cp2Mo2(μ-SMe)4, 3. Dahl and co-workers had shown previously that the cations of the two iron complexes display significant shortening of the metal---metal distance (47 pm and 36 pm, respectively, for 1 and 2) due to removal of an electron from an antibonding M---M orbital from the neutral compounds. By comparison, the structure of 3 is virtually unchanged upon one-electron oxidation. Surprisingly, the greater structural changes of 1 and 2 do not lead to lower heterogeneous electron-transfer rates than 3. In acetonitrile at Pt or mercury electrodes all three complexes have ks values, measured by cyclic voltammetry, of ca. 0.2 cm s−1. Several possible reasons for this behavior are discussed.en_US
dc.format.extent37365 bytesen_US
dc.format.mimetypeapplication/pdfen_US
dc.language.isoen_USen_US
dc.publisherElsevier: Journal of Electroanalytical Chemistryen_US
dc.relation.ispartofseriesStructural Consequences of Electron-Transfer Reactionsen_US
dc.relation.ispartofseriesXIVen_US
dc.subjectBinuclear complexesen_US
dc.subjectElectron transferen_US
dc.subjectStructural changesen_US
dc.titleFast charge-transfer reactions of binuclear complexes undergoing large changes in metal---metal bond lengthsen_US
dc.typeAbstracten_US
dc.identifier.urlhttp://dx.doi.org/10.1016/0022-0728(87)80283-8


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