Laboratoire de Chimie et Biologie des Métaux, UMR 5249-Université Grenoble I-CNRS-CEA CEA Grenoble, 17 Avenue des Martyrs, 38054 Grenoble, France.
Inorg Chem. 2012 Feb 20;51(4):2222-30. doi: 10.1021/ic2022159. Epub 2012 Feb 1.
In our research program aiming to develop new ruthenium-based polypyridine catalysts for oxidation we were interested in combining a photosensitizer and a catalytic fragment within the same complex to achieve catalytic light-driven oxidation. To respond to the lack of such conjugates, we report here a new catalytic system capable of using light to activate water molecules in order to perform selective sulfide oxygenation into sulfoxide via an oxygen atom transfer from H(2)O to the substrate with a TON of up to 197 ± 6. On the basis of electrochemical and photophysical studies, a proton-coupled electron-transfer process yielding to an oxidant Ru(IV)-oxo species was proposed. In particular, the synergistic effect between both partners in the dyad yielding a more efficient catalyst compared to the bimolecular system is highlighted.
在我们旨在开发新型基于钌的多吡啶催化剂用于氧化的研究计划中，我们有兴趣将光敏剂和催化片段结合在同一个配合物中，以实现催化光驱动氧化。为了应对缺乏此类共轭物的问题，我们在这里报告了一个新的催化体系，该体系能够利用光激活水分子，从而通过从 H(2)O 到底物的氧原子转移将选择性地将硫化物氧化成亚砜，TON 高达 197 ± 6。基于电化学和光物理研究，提出了质子耦合电子转移过程生成氧化剂 Ru(IV)-氧物种。特别是，在二联体中两个配体之间的协同作用产生了比双分子体系更有效的催化剂。
