Formation of the syn isomer of [Fe(IV)(Oanti)(TMC)(NCMe)](2+) in the reaction of Lewis acids with the side-on bound peroxo ligand in [Fe(III)(η(2)-O2)(TMC)](.)

Jai Prakash; Lawrence Que

doi:10.1039/c6cc01660j

Formation of the syn isomer of [Fe(IV)(Oanti)(TMC)(NCMe)](2+) in the reaction of Lewis acids with the side-on bound peroxo ligand in [Fe(III)(η(2)-O2)(TMC)](.)

Chem Commun (Camb). 2016 Jun 21;52(52):8146-8. doi: 10.1039/c6cc01660j.

Authors

Jai Prakash¹, Lawrence Que¹

Affiliation

¹ Department of Chemistry and Centre for Metals in Biocatalysis, University of Minnesota, 207 Pleasant St. SE, Minneapolis, Minnesota 55455, USA. [email protected].

PMID: 27273175
DOI: 10.1039/c6cc01660j

Abstract

We demonstrate that the reactions of [Fe(III)(η(2)-O2)(TMC)](+) (TMC = tetramethylcyclam) with Lewis acids (H(+) and NO(+)) afford the recently described syn isomer of [Fe(IV)(O)(TMC)(NCMe)](2+) (and not the anti isomer as had been tacitly assumed). This outcome is a logical consequence of the fact that the side-on peroxo ligand is bound to the syn face of the Fe(TMC) unit in the precursor.