Abstract
MUCH attention has been given to electron transfer between metal ions through organic ligands, particularly the chromium(II)–cobalt(III) reduction1–5. Experiments have shown that conjugated dicarboxy ligands such as fumarate may provide two paths for the electron transfer: the ligand may be attacked by the reductant at either of the two COO groups. Attack at the remote carboxyl is evidenced by both an acid-independent and an acid-dependent term in the rate laws, while attack at the carboxyl group co-ordinated to the oxidant is acid-independent. The role of the proton in the acid-dependent reaction is to increase conjugation between the remote carboxyl and the cobalt(III) centre, for example: 
and an examination of the induced ester hydrolysis in experiments with vanadium(II) and half-ester complexes6 has shown that the remote attack involves bond formation between the reductant and the carbonyl oxygen of the carboxyl group: 
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References
Taube, H., J. Amer. Chem. Soc., 77, 4481 (1955).
Fraser, R. T. M., Sebera, D. K., and Taube, H., J. Amer. Chem. Soc., 81, 2906 (1959).
Fraser, R. T. M., J. Amer. Chem. Soc., 83, 564 (1961).
Sebera, D. K., and Taube, H., J. Amer. Chem. Soc., 83, 1785 (1961).
Fraser, R. T. M., Inorg. Chem., 3, 255 (1964).
Fraser, R. T. M., and Taube, H., J. Amer. Chem. Soc., 81, 5514 (1959).
Sen, D. N., Mizushima, S., Curran, C., and Ouagliano, J. V., J. Amer. Chem. Soc., 77, 211 (1955).
Drouin, M., Mathieu, J., and Poulet, H., J. Chim. Phys., 58, 322 (1961).
Bertin, E. P., Penland, R. B., Mizushima, S., Curran, C., and Ouagliano, J. V., J. Amer. Chem. Soc., 81, 3818 (1959).
Hunt, J. P., Rutenberg, A. C., and Taube, H., J. Amer. Chem. Soc., 74, 268 (1952).
Bunton, C. A., and Llewellyn, D. R., J. Chem. Soc., 1692 (1953).
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FRASER, R. Point of Reductant Attack in Electron Transfer through Carboxylate Mediators. Nature 202, 691–692 (1964). https://doi.org/10.1038/202691a0
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DOI: https://doi.org/10.1038/202691a0
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