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

A sterically accessible tert-butyl-substituted dipyrrinato di-iron(II) complex [(L-tBu)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 Feu' species was confirmed by Fe-57 Mossbauer spectroscopy. Crystallographic characterization revealed two possible oxidation products: (1) a terminal iron iminyl from aryl azides bearing ortho isopropyl substituents, (L-tBu)FeCl(center dot NC6H3-2,6-Pr-i(2)); or (2) a bridging di-iron imido arising from reaction with 3,S-bis(trifluoromethyl)aryl azide, [(L-tBu)FeCl](2)(mu-NC6H3-3,5-(CF3)(2)). Similar to the previously reported (L-Ar)FeCl((NC6H4)-N-center dot-4-Bu-t), the monomeric iron imido is best described as a high-spin Fein 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 F-III 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 [((tBu))FeCl](2)(mu-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.