Diradical Generation via Relayed Proton-Coupled Electron Transfer
Qianqian Shi, Zhipeng Pei, Jinshuai Song, Shijun Li, Donghui Wei, Michelle L. Coote, Yu Lan
Abstract
Diradical generation followed by radical-radical cross-coupling is a powerful synthetic tool, but its detailed mechanism has yet to be established. Herein, we proposed and confirmed a new model named relayed proton-coupled electron transfer (relayed-PCET) for diradical generation, which could open a door for new radical-radical cross-coupling reactions. Quantum mechanics calculations were performed on a selected carbene-mediated diradical cross-coupling reaction model and a designed model, and the exact electronic structural changes during the radical processes have been observed for the first time.
Topics & Concepts
DiradicalChemistryElectron transferCoupling (piping)CarbeneProtonPhotochemistryElectronChemical physicsProton-coupled electron transferComputational chemistryRadicalAtomic physicsQuantum mechanicsCatalysisPhysicsExcited stateOrganic chemistrySinglet stateMechanical engineeringEngineeringRadical Photochemical ReactionsCatalytic C–H Functionalization MethodsCO2 Reduction Techniques and Catalysts