Octahedral iron(iv)–tosylimido complexes exhibiting single electron-oxidation reactivity

Abstract

Octahedral iron(iv) tosylimido complexes based in the tacn ligand scaffold exhibit single electron oxidation reactivity.

Fe-Catalyzed Aziridination Is Governed by the Electron Affinity of the Active Imido-Iron Species

“…The Fe-NTs distances obtained for 3 2 IV =NTs 2+ and 3 1 IV =NTs 2+ are in the expected range (ca 1.71-1.73 Å, Table S2) and consistent with values already published 21,31,58,59 for 3 1 IV =NTs 2+ . In agreement with these previous papers the spin densities reveal a strong radical character on the NTs nitrogen (Table S2), especially for the triplet state, reflecting the high covalency of Fe-imido bonds 59 as can be seen on the Kohn-Sham orbitals displayed in Figure S3 and S4.…”

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

“…Somewhat related substrate-to-catalyst single-electron transfer coupled to σ-bond formation has been observed in some other instances though. Iron-tosylimido complexes acting as (iron-centered) one-electron oxidants toward thioanisole and aromatic amines have recently been disclosed, producing sulfonimides/sulfonamides and oxidized amines, respectively. , Recently, electron transfer from p -methoxythioanisole to [Fe V (TAML sq )­(NTs)] was observed prior to S–N bond formation . Moreover, single-electron transfer from styrene to an Fe­(IV)-nitride was proposed to occur during C–N bond formation and was found to be coupled to a spin state change from the singlet to triplet surface .…”

Inspiration from Nature: Influence of Engineered Ligand Scaffolds and Auxiliary Factors on the Reactivity of Biomimetic Oxidants

“…In addition to the synthetic models of iron-amides, , iron-imides, − ,,− and iron-nitrides , prevalent in the literature, even high-valent iron­(V)-imido species has been reported recently. − Similar to the generation of the iron­(V)-oxo TAML (tetraamido macrocyclic ligand) complexes, − an iron­(V)-imido TAML complex was synthesized by Hong et al by addition of three equivalents of N -tosylimidophenyliodinane (PhINTs) to the ferric precursor complex at 15 °C …”