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Electrochemical proton reduction by thiolate-bridged hexacarbonyldiiron clusters

Abstract : The reduction of Fe2(μ-SC6H4S)(CO) 6 (1) at glassy carbon electrode appears chemically reversible (E1/2 = -1.44 V vs. Fc in Bu4NPF6-CH 2Cl2, ks,h ∼ 5 × 10-3 cm s-1) and actually consists of two overlapping one-electron transfers with the second transfer slightly more favorable than the first (E 02-E01 ∼ 35 mV). Apparently, the reduction of Fe2(μ-SCH2C6H 4CH2S)(CO)6 (2) is also a two-electron process (E1/2 = -1.68 V vs. Fc in Bu4NPF6-CH 2Cl2), but 22- decomposes on the voltammetric time scale. For both 1 and 2, the electrochemical reduction of the neutral cluster generates intermediate species which further catalyze proton reduction in acid-containing electrolyte (i.e., HBF4 in Bu4NPF 6-CH2Cl2). Unfortunately voltammetry also reveals a catalytic cycle for electrochemical proton reduction either slow or complicated by side reactions. © 2003 Elsevier B.V. All rights reserved.
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https://hal.univ-brest.fr/hal-01763872
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Submitted on : Wednesday, April 11, 2018 - 2:58:21 PM
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Jean-François Capon, Frederic Gloaguen, Philippe Schollhammer, Jean Talarmin. Electrochemical proton reduction by thiolate-bridged hexacarbonyldiiron clusters. Journal of Electroanalytical Chemistry, Elsevier 2004, 566 (2), pp.241-247. ⟨10.1016/j.jelechem.2003.11.032⟩. ⟨hal-01763872⟩

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