A tale of two topological isomers: Uptuning [Fe^IV(O)(Me₄cyclam)]²⁺ for olefin epoxidation.

ABSTRACT: TMC-anti and TMC-syn, the two topological isomers of [Fe^IV(O)(TMC)(CH₃CN)]²⁺ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, or Me₄cyclam), differ in the orientations of their Fe^IV=O units relative to the four methyl groups of the TMC ligand framework. The Fe^IV=O unit of TMC-anti points away from the four methyl groups, while that of TMC-syn is surrounded by the methyl groups, resulting in differences in their oxidative reactivities. TMC-syn reacts with HAT (hydrogen atom transfer) substrates at 1.3- to 3-fold faster rates than TMC-anti, but the reactivity difference increases dramatically in oxygen-atom transfer reactions. R₂S substrates are oxidized into R

SUBMITTER: Chandra B 

PROVIDER: S-EPMC10962992 | biostudies-literature | 2024 Mar

REPOSITORIES: biostudies-literature