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Article Dans Une Revue Journal of electroanalytical chemistry and interfacial electrochemistry Année : 2006

Activation of proton by the two-electron reduction of a di-iron organometallic complex

Résumé

Fe2(bdt)(CO)6 (1) (bdt = benzenedithiolate) exhibits a chemically reversible two-electronreduction at −1.27 V vs. Fc+/0 in CH3CN + Bu4NPF6 electrolyte. The increase in height of the reduction wave of complex1 upon increasing the concentration of toluenesulfonic acid (pKa ∼ 8 in CH3CN) is consistent with a catalysis of the protonreduction reaction (kcat ∼ 500 M−1 s−1). The reaction scheme, derived from the simulation of the voltammetric responses, involves the initial formation of the dianion 12− followed by two successive reactions with acid. The last protonation step is the rate determining step in the catalytic cycle. Using experiments conducted with acetic acid (pKa ∼ 23 in CH3CN), we further shown that the intermediate species 1H− is a significantly weaker base than the dianion 12−.

Dates et versions

hal-00700128 , version 1 (22-05-2012)

Identifiants

Citer

Jean-François Capon, Frederic Gloaguen, Philippe P. Schollhammer, Jean Talarmin. Activation of proton by the two-electron reduction of a di-iron organometallic complex. Journal of electroanalytical chemistry and interfacial electrochemistry, 2006, 595 (1), pp.47-52. ⟨10.1016/j.jelechem.2006.06.005⟩. ⟨hal-00700128⟩
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