Electronically Asynchronous Transition States for C–N Bond Formation by Electrophilic <b> [Co <sup>III</sup> (TAML)] </b> -Nitrene Radical Complexes Involving Substrate-to-Ligand Single-Electron Transfer and a Cobalt-Centered Spin Shuttle
Nicolaas P. van Leest, Martijn A. Tepaske, Bas Venderbosch, Jean‐Pierre H. Oudsen, Moniek Tromp, Jarl Ivar van der Vlugt, Bas de Bruin
Abstract
= 1) cobalt(III) center. Hence, the TAML moiety can be regarded to act as a transient electron acceptor, the cobalt center behaves as a spin shuttle, and the nitrene radical acts as a nucleophile. Such a mechanism was hitherto unknown for cobalt-catalyzed hypovalent group transfer and the more general transition-metal-catalyzed nitrene transfer to alkenes but is now shown to complement the known concerted and stepwise mechanisms for N-group transfer.
Topics & Concepts
NitreneChemistryRadicalPhotochemistryLigand (biochemistry)Electron transferElectrophileRadical ionCatalysisMedicinal chemistryStereochemistryOrganic chemistryIonReceptorBiochemistrySynthesis and Catalytic ReactionsCatalytic C–H Functionalization MethodsMetal-Catalyzed Oxygenation Mechanisms