Journal of Electroanalytical Chemistry
The one-electron reduction of CpFe(CO)2CH3 has been investigated by voltammetry and Fourier transform IR spectroelectrochemistry. The reduction initiates the insertion of CO ligand in the FeCH3 bond. The dissociation of a CO group proceeds in a parallel reaction. Reaction intermediates, the acyl derivative and released CO, form the radical anion of a complex CpFe(CO)2(COCH3) which is able to reduce the parent compound. The reversible redox potential − 1.8 V of CpFe(CO)2(COCH3) allows the regeneration of its radical anion which drives a catalytic cycle. The lifetime of intermediates is shortened by side reactions, one of which is the migration of the acyl group from the central atom to the cyclopentadienyl ring. This explains the apparent discrepancy between products observed in preparative scale electrolysis and the absence of catalytic effects in routine voltammetric experiments.
Amatore, C.; Bayachou, Mekki; Verpeaux, J. N.; Pospisil, L.; and Fiedler, J., "Electrochemical Carbonylation of Organoiron Methyl Complex: A Study of Reaction Intermediates" (1995). Chemistry Faculty Publications. 310.
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