Unmasking Steps in Intramolecular Aromatic Hydroxylation by a Synthetic Nonheme Oxoiron(IV) Complex.

ABSTRACT: In this study, a methyl group on the classic tetramethylcyclam (TMC) ligand framework is replaced with a benzylic group to form the metastable [Fe^IV (O_syn )(Bn3MC)]²⁺ (2-syn; Bn3MC=1-benzyl-4,8,11-trimethyl-1,4,8,11-tetraazacyclotetradecane) species at -40 °C. The decay of 2-syn with time at 25 °C allows the unprecedented monitoring of the steps involved in the intramolecular hydroxylation of the ligand phenyl ring to form the major Fe^III -OAr product 3. At the same time, the Fe^II (Bn3MC)²⁺ (1) precursor to 2-syn is re-generated in a 1:2 molar ratio relative to 3, accounting for the first time for all the electrons involved and all the Fe species derived from 2-syn as shown in the following balanced equation: 3 [Fe^IV

SUBMITTER: Sheng Y 

PROVIDER: S-EPMC8429247 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature