Activation of proton by the two-electron reduction of a di-iron organometallic complex
| Autor: | Jean-François Capon, Philippe Schollhammer, Jean Talarmin, Frédéric Gloaguen |
|---|---|
| Přispěvatelé: | Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC) |
| Jazyk: | angličtina |
| Rok vydání: | 2006 |
| Předmět: |
Reaction mechanism
010405 organic chemistry Chemistry General Chemical Engineering Iron Inorganic chemistry Voltammetry simulation Homogeneous catalysis Protonation 010402 general chemistry Rate-determining step 01 natural sciences Medicinal chemistry Redox 0104 chemical sciences Analytical Chemistry Catalysis Electron transfer Catalytic cycle Electrochemistry PIEnergie Hydrogenase model Protonreduction |
| Zdroj: | Journal of electroanalytical chemistry and interfacial electrochemistry Journal of electroanalytical chemistry and interfacial electrochemistry, Elsevier, 2006, 595 (1), pp.47-52. ⟨10.1016/j.jelechem.2006.06.005⟩ |
| ISSN: | 0022-0728 |
| DOI: | 10.1016/j.jelechem.2006.06.005⟩ |
| Popis: | Fe 2 (bdt)(CO) 6 ( 1 ) (bdt = benzenedithiolate) exhibits a chemically reversible two-electron reduction at −1.27 V vs. Fc +/0 in CH 3 CN + Bu 4 NPF 6 electrolyte. The increase in height of the reduction wave of complex 1 upon increasing the concentration of toluenesulfonic acid (p K a ∼ 8 in CH 3 CN) is consistent with a catalysis of the proton reduction reaction ( k cat ∼ 500 M −1 s −1 ). The reaction scheme, derived from the simulation of the voltammetric responses, involves the initial formation of the dianion 1 2− 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 (p K a ∼ 23 in CH 3 CN), we further shown that the intermediate species 1 H − is a significantly weaker base than the dianion 1 2− . |
| Databáze: | OpenAIRE |
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