Laboratoire d'Electrochimie Moléculaire, Unité Mixte de Recherche Université - CNRS No 7591, Université Paris Diderot, Bâtiment Lavoisier, 15 rue Jean de Baïf, 75205 Paris Cedex 13, France.
Faraday Discuss. 2011;148:83-95; discussion 97-108. doi: 10.1039/c004276e.
Water-bound metal (M) complexes play a central role in the catalytic centers of natural systems such as Photosystem II (PSII), superoxide dismutase, cytochrome c oxidase and others. In these systems, electron transfer reactions involving the metal center are coupled to proton transfers. Besides its fundamental interest, comprehension of these reactions and of possible bio-inspired catalytic devices is an additional motivation for studying the coupling between proton and electron transfer (proton-coupled electron transfers, PCET), starting with an aqua-M(II)/hydroxo-M(III) couple, and going to higher oxidation degrees as in the case of PSII (hydroxo-M(III)/oxo-M(IV) couple). Factors that determine the occurrence of the stepwise and concerted pathways are recalled from the illustrating example of a recently described mononuclear osmium complex, thus opening perspectives for further studies of the biomimicking complex. PCET in a mononuclear aqua/hydroxo manganese couple was then studied using the electrochemical approach.
水合金属 (M) 配合物在光合作用系统 II (PSII)、超氧化物歧化酶、细胞色素 c 氧化酶等天然系统的催化中心中起着核心作用。在这些系统中，涉及金属中心的电子转移反应与质子转移耦合。除了其基本兴趣之外，理解这些反应和可能的仿生催化装置是研究质子和电子转移（质子耦合电子转移，PCET）耦合的另一个动机，从水合-M(II)/羟基金属-M(III) 配合物开始，并上升到更高的氧化态，如 PSII（羟基金属-M(III)/氧基金属-M(IV) 配合物）的情况。从最近描述的单核锇配合物的说明性示例中回忆起决定逐步和协同途径发生的因素，从而为进一步研究仿生配合物开辟了前景。然后使用电化学方法研究了单核水合/羟基金属锰配合物中的 PCET。
