Fast charge-transfer reactions of binuclear complexes undergoing large changes in metal---metal bond lengths

Show full item record

Title: Fast charge-transfer reactions of binuclear complexes undergoing large changes in metal---metal bond lengths
Author: Gennett, Thomas; Geiger, William; Willet, Brian; Anson, Fred
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.
Record URI: http://hdl.handle.net/1850/2152
Publishers URL: http://dx.doi.org/10.1016/0022-0728(87)80283-8
Date: 1987-05-08

Files in this item

Files Size Format View

An open access version of this file is not available. Check "Publisher URL" field for access

This item appears in the following Collection(s)

Show full item record

Search RIT DML


Advanced Search

Browse