Nonheme Iron Imido Complexes Bearing a Non-Innocent Ligand: A Synthetic Chameleon Species in Oxidation Reactions

High-valent iron-imido complexes can perform C−H activation and sulfimidation reactions, but are far less studied than the more ubiquitous iron-oxo species. As case studies, we have looked at a recently published iron(V)-imido ligand π-cation radical complex, which is formally an iron(VI)-imido complex [Fe^V(NTs)(TAML^+.)] (1; NTs=tosylimido), and an iron(V)-imido complex [Fe^V(NTs)(TAML)]⁻ (2). Using a theoretical approach, we found that they have multiple energetically close-lying electromers, sometimes even without changing spin states, reminiscent of the so-called Compound I in Cytochrome P450. When studying their reactivity theoretically, it is indeed found that their electronic structures may change to perform efficient oxidations, emulating the multi-spin state reactivity in Fe^IVO systems. This is actually in contrast to the known [Fe^V(O)(TAML)]⁻ species (3), where the reactions occur only on the ground spin state. We also looked into the whole reaction pathway for the C−H bond activation of 1,4-cyclohexadiene by these intermediates to reproduce the experimentally observed products, including steps that usually attract no interest (neither theoretically nor experimentally) due to their non-rate-limiting status and fast reactivity. A new “clustering non-rebound mechanism” is presented for this C−H activation reaction.