Unmasking the Iron-Oxo Bond of the [(Ligand)Fe-OIAr]^2+/+ Complexes.

ABSTRACT: ArIO (ArI = 2-(^tBuSO₂)C₆H₄I) is an oxidant used to oxidize Fe^II species to their Fe^IV-oxo state, enabling hydrogen-atom transfer (HAT) and oxygen-atom transfer (OAT) reactions at low energy barriers. ArIO, as a ligand, generates masked Feⁿ═O species of the type Fe^(n-2)-OIAr. Herein, we used gas-phase ion-molecule reactions and DFT calculations to explore the properties of masked iron-oxo species and to understand their unmasking mechanisms. The theory shows that the I-O bond cleavage in [(TPA)Fe^IVO(ArIO)]²⁺ (1²⁺, TPA = tris(2-pyridylmethyl)amine)) is highly endothermic; therefore, it can be achieved only in collision-induced dissociation of 1

SUBMITTER: Tripodi GL 

PROVIDER: S-EPMC9460779 | biostudies-literature | 2022 Sep

REPOSITORIES: biostudies-literature