Construction of highly efficient and highly selective catalytic oxidation systems based on proton-coupled electron transfer

我们利用Ru(II)-吡啶胺-水络合物在水缓冲溶液中作为催化剂，建立了高效、高选择性的有机底物催化氧化体系。在这些反应中，钌(IV)-氧配合物通过质子耦合电子转移形成，并通过光谱和晶体学方法以及DFT计算对其进行了表征。在这项研究中，我们已经澄清了Ru(IV)-氧配合物的自旋态不影响它们的反应性。我们还首次成功地直接观察了C-H羟基化反应中的氧回弹机理，并从动力学分析的角度阐明了C-H氧化的反应机理。

We have established highly efficient and highly selective catalytic oxidation systems for organic substrates using Ru(II)-pyridylamine-aqua complexes as catalysts in aqueous buffer solutions. In those reactions, Ru(IV)-oxo complexes were formed via proton-coupled electron transfer and their characterization were made by spectroscopic and crystallographic methods and DFT calculations. In this research, we have clarified that the spin states of Ru(IV)-oxo complexes do not affect their reactivity. We have also succeeded in the direct observation of the oxygen-rebound mechanism in C-H hydroxylation for the first time and elucidated the reaction mechanism of C-H oxidation in the light of kinetic analysis.