Characterization of a Ferryl Flip in Electronically Tuned Nonheme Complexes. Consequences in Hydrogen Atom Transfer Reactivity.

ABSTRACT: Two oxoiron(IV) isomers (^R 2a and ^R 2b) of general formula [Fe^IV (O)(^R PyNMe₃ )(CH₃ CN)]²⁺ are obtained by reaction of their iron(II) precursor with NBu₄ IO₄ . The two isomers differ in the position of the oxo ligand, cis and trans to the pyridine donor. The mechanism of isomerization between ^R 2a and ^R 2b has been determined by kinetic and computational analyses uncovering an unprecedented path for interconversion of geometrical oxoiron(IV) isomers. The activity of the two oxoiron(IV) isomers in hydrogen atom transfer (HAT) reactions shows that ^R 2a reacts one order of magnitude faster than ^R 2b, which is explained by a repulsive noncovalent intera

SUBMITTER: Dantignana V 

PROVIDER: S-EPMC10107328 | biostudies-literature | 2023 Jan

REPOSITORIES: biostudies-literature