[Ru(bda)(L)₂]催化水氧化的机制：“蓝色二聚体”的回归

Mechanism of water oxidation by [Ru(bda)(L)2]: the return of the "blue dimer".

作者信息

Concepcion Javier J, Zhong Diane K, Szalda David J, Muckerman James T, Fujita Etsuko

机构信息

Department of Chemistry, Brookhaven National Laboratory, Upton, NY 11973-5000, USA.

出版信息

Chem Commun (Camb). 2015 Mar 7;51(19):4105-8. doi: 10.1039/c4cc07968j.

DOI:10.1039/c4cc07968j

PMID:25670391

Abstract

We describe here a combined solution-surface-DFT calculations study for complexes of the type [Ru(bda)(L)2] including X-ray structure of intermediates and their reactivity, as well as pH-dependent electrochemistry and spectroelectrochemistry. These studies shed light on the mechanism of water oxidation by [Ru(bda)(L)2], revealing key features unavailable from solution studies with sacrificial oxidants.

摘要

我们在此描述了针对[Ru(bda)(L)₂]类型配合物的溶液 - 表面 - 密度泛函理论（DFT）计算联合研究，包括中间体的X射线结构及其反应活性，以及pH依赖性电化学和光谱电化学。这些研究揭示了[Ru(bda)(L)₂]催化水氧化的机制，揭示了使用牺牲性氧化剂进行溶液研究时无法获得的关键特征。