Department of Photochemistry and Molecular Science, Uppsala University, Box 523, SE-751 20 Uppsala, Sweden.
J Am Chem Soc. 2011 Aug 31;133(34):13224-7. doi: 10.1021/ja203483j. Epub 2011 Aug 9.
Proton-coupled electron transfer (PCET) was examined in a series of biomimetic, covalently linked Ru(II)(bpy)(3)-tyrosine complexes where the phenolic proton was H-bonded to an internal base (a benzimidazyl or pyridyl group). Photooxidation in laser flash/quench experiments generated the Ru(III) species, which triggered long-range electron transfer from the tyrosine group concerted with short-range proton transfer to the base. The results give an experimental demonstration of the strong dependence of the rate constant and kinetic isotope effect for this intramolecular PCET reaction on the effective proton transfer distance, as reflected by the experimentally determined proton donor-acceptor distance.
质子耦合电子转移 (PCET) 在一系列仿生的、共价连接的 Ru(II)(bpy)(3)-酪氨酸复合物中进行了研究，其中酚质子与内部碱（苯并咪唑或吡啶基团）形成氢键。激光闪光/猝灭实验中的光氧化生成了 Ru(III)物种，这引发了酪氨酸基团与短程质子转移到碱的协同远程电子转移。结果为该分子内 PCET 反应的速率常数和动力学同位素效应对有效质子转移距离的强烈依赖性提供了实验证明，这反映在实验确定的质子给体-受体距离上。
