Characterization of Iron-Imido Species Relevant for N‑Group Transfer Chemistry

A sterically accessible tert-butyl-substituted dipyrrinato di-iron­(II) complex [( tBuL)­FeCl]2 possessing two bridging chloride atoms was synthesized from the previously reported solvento adduct. Upon treatment with aryl azides, the formation of high-spin FeIII species was confirmed by 57Fe Mössbauer spectroscopy. Crystallographic characterization revealed two possible oxidation products: (1) a terminal iron iminyl from aryl azides bearing ortho isopropyl substituents, ( tBuL)­FeCl­(•NC6H3-2,6- i Pr2); or (2) a bridging di-iron imido arising from reaction with 3,5-bis­(trifluoromethyl)­aryl azide, [( tBuL)­FeCl]2(μ-NC6H3-3,5-(CF3)2). Similar to the previously reported (ArL)­FeCl­(•NC6H4-4- t Bu), the monomeric iron imido is best described as a high-spin FeIII antiferromagnetically coupled to an iminyl radical, affording an S = 2 spin state as confirmed by SQUID magnetometry. The di-iron imido possesses an S = 0 ground state, arising from two high-spin FeIII centers weakly antiferromagnetically coupled through the bridging imido ligand. The terminal iron iminyl complex undergoes facile decomposition via intra- or intermolecular hydrogen-atom abstraction (HAA) from an imido aryl ortho isopropyl group, or from 1,4-cyclohexadiene, respectively. The bridging di-iron imido is a competent N-group transfer reagent to cyclic internal olefins as well as styrene. Although solid-state magnetometry indicates an antiferromagnetic interaction between the two iron centers (J = −108.7 cm–1) in [( tBuL)­FeCl]2(μ-NC6H3-3,5-(CF3)2), we demonstrate that in solution the bridging imido can facilitate HAA as well as dissociate into a terminal iminyl species, which then can promote HAA. In situ monitoring reveals the di-iron bridging imido is a catalytically competent intermediate, one of several iron complexes observed in the amination of C–H bond substrates or styrene aziridination.