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

[Image: see text] The oxidation state of the redox noninnocent tetra-amido macrocyclic ligand (TAML) scaffold was recently shown to affect the formation of nitrene radical species on cobalt(III) upon reaction with PhI=NNs [ N. P. van Leest; J. Am. Chem. Soc.2020, 142, 552−56331846578]. For the neutral [Co(III)(TAML(sq))] complex, this leads to the doublet (S = 1/2) mono-nitrene radical species [Co(III)(TAML(q))(N(•)Ns)(Y)] (bearing an unidentified sixth ligand Y in at least the frozen state), 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, cyclohexane, and 1-hexene under mild and even aerobic (for [Co(III)(TAML(red))](–)) conditions. Experimental (Hammett plots; [Co(III)(TAML)]-nitrene radical formation and quantification under catalytic conditions; single-turnover experiments; and tests regarding catalyst decomposition, radical inhibition, and radical trapping) in combination with computational (density functional theory (DFT), N-electron valence state perturbation theory corrected complete active space self-consistent field (NEVPT2-CASSCF)) studies reveal that [Co(III)(TAML(q))(N(•)Ns)(Y)], [Co(III)(TAML(q))(N(•)Ns)(2)](–), and [Co(III)(TAML(sq))(N(•)Ns)](–) are key electrophilic intermediates in 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 the (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 the formation of an amido-γ-benzyl radical (NsN(–)–CH(2)–(•)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 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.