dc.contributor.author | Gennett, Thomas | en_US |
dc.contributor.author | Geiger, William | en_US |
dc.contributor.author | Willet, Brian | en_US |
dc.contributor.author | Anson, Fred | en_US |
dc.date.accessioned | 2006-07-19T19:34:25Z | en_US |
dc.date.available | 2006-07-19T19:34:25Z | en_US |
dc.date.issued | 1987-05-08 | en_US |
dc.identifier.citation | Journal of Electroanalytical Chemistry 222N1-2 (1987) 151-160 | en_US |
dc.identifier.issn | 0022-0728 | en_US |
dc.identifier.uri | http://hdl.handle.net/1850/2152 | en_US |
dc.description.abstract | Heterogeneous 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.extent | 37365 bytes | en_US |
dc.format.mimetype | application/pdf | en_US |
dc.language.iso | en_US | en_US |
dc.publisher | Elsevier: Journal of Electroanalytical Chemistry | en_US |
dc.relation.ispartofseries | Structural Consequences of Electron-Transfer Reactions | en_US |
dc.relation.ispartofseries | XIV | en_US |
dc.subject | Binuclear complexes | en_US |
dc.subject | Electron transfer | en_US |
dc.subject | Structural changes | en_US |
dc.title | Fast charge-transfer reactions of binuclear complexes undergoing large changes in metal---metal bond lengths | en_US |
dc.type | Abstract | en_US |
dc.identifier.url | http://dx.doi.org/10.1016/0022-0728(87)80283-8 | |