Electronically Asynchronous Transition States for C-N Bond Formation by Electrophilic [Coᴵᴵᴵ(TAML)]-Nitrene Radical Complexes Involving Substrate-to-Ligand Single-Electron Transfer and a Cobalt-Centered Spin Shuttle

The oxidation state of the redox non-innocent TAML (Tetra-Amido Macrocyclic Ligand) scaffold was recently shown to affect the formation of nitrene radical species on cobalt(III) upon reaction with PhI=NNs [J. Am. Chem. Soc. 2020, DOI: 10.1021/jacs.9b11715]. For the neutral [Co^III(TAMLsq)] complex this leads to the doublet (S = ½) mono-nitrene radical species [Co^III(TAMLq)(N^•Ns)], while a triplet (S = 1) bis-nitrene radical species [Co^III(TAML^q)(N^•Ns)₂]^‒ is generated from the anionic [Co^III(TAML^red)]^‒ complex. The one-electron reduced Fischer-type nitrene radicals (N^•Ns^‒) are formed through single (mono-nitrene) or double (bis-nitrene) ligand-to-substrate single-electron transfer (SET). In this work we describe the reactivity and mechanisms of these nitrene radical complexes in catalytic aziridination. We report that [Co^III(TAML^sq)] and [Co^III(TAML^red)]^‒ are both effective catalysts for chemoselective (C=C versus C‒H bonds) and diastereoselective aziridination of styrene derivatives, cyclohexene and 1-hexene under mild and even aerobic (for [Co^III(TAML^red)]^‒) conditions. Experimental (Hammett plots, radical inhibition, catalyst decomposition tests) and computational (DFT, CASSCF) studies reveal that [Co^III(TAML^q)(N^•Ns)], [Co^III(TAML^q)(N^•Ns)₂]^‒ and [Co^III(TAML^sq)(N^•Ns)]^– are key electrophilic intermediates in the aziridination reactions. Surprisingly, the electrophilic one-electron reduced Fischer-type nitrene radicals do not react as would be expected for nitrene radicals (i.e. via radical addition and radical rebound). Instead, nitrene transfer proceeds through unusual electronically asynchronous transition states, in which (partial) styrene substrate to TAML ligand (single) electron transfer precedes C-N coupling. The actual C-N bond formation processes are best described as involving a nucleophilic attack of the nitrene (radical) lone pair at the thus (partially) formed styrene radical cation. These processes are coupled to TAML-to-cobalt and cobalt-to-nitrene single-electron transfer, effectively leading to formation of an amido-[gamma]-benzyl radical (Ns–N–CH₂–^•CH–Ph) bound to an intermediate spin (S = 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 for (cobalt catalyzed) nitrene transfer was hitherto unknown and complements the known concerted and stepwise mechanisms for N-group transfer.