The mechanism of the hydroxylation of benzene by an iron(II) bis(NHC) complex, [Fe-II(NCCN)(CH3CN)(2)] (PF6)(2) (1; NCCN = bis(o-imidazol-2-ylidenepyridine)methane), in the presence of hydrogen peroxide was investigated. The invariance of the catalytic system towards the presence of radical scavengers and an inverse intermolecular kinetic isotope effect (ICIE) allow to rule out a hydrogen abstraction pathway. Additionally, using 1,3,5-[D-3]benzene as substrate, NIH-shift products were detected, resembling the reactivity of naturally occurring enzymes and some molecular biomimetic iron complexes. Supported by density functional theory calculations, the aromatic hydroxylation reaction is proposed to proceed via an iron-arene sigma-complex as intermediate species. (C) 2017 Elsevier Inc. All rights reserved.