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Deformylation Reaction by a Nonheme Manganese(III)–Peroxo Complex via Initial Hydrogen‐Atom Abstraction
Author(s) -
Barman Prasenjit,
Upadhyay Pranav,
Faponle Abayomi S.,
Kumar Jitendra,
Nag Sayanta Sekhar,
Kumar Devesh,
Sastri Chivukula V.,
de Visser Sam P.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201604412
Subject(s) - reactivity (psychology) , chemistry , nucleophile , manganese , hydrogen atom abstraction , catalysis , ligand (biochemistry) , reaction mechanism , kinetic isotope effect , combinatorial chemistry , photochemistry , hydrogen , organic chemistry , deuterium , alternative medicine , receptor , medicine , biochemistry , physics , pathology , quantum mechanics
Metal–peroxo intermediates are key species in the catalytic cycles of nonheme metalloenzymes, but their chemical properties and reactivity patterns are still poorly understood. The synthesis and characterization of a manganese(III)–peroxo complex with a pentadentate bispidine ligand system and its reactivity with aldehydes was studied. Manganese(III)–peroxo can react through hydrogen‐atom abstraction reactions instead of the commonly proposed nucleophilic addition reaction. Evidence of the mechanism comes from experiments which identify a primary kinetic isotope effect of 5.4 for the deformylation reaction. Computational modeling supports the established mechanism and identifies the origin of the reactivity preference of hydrogen‐atom abstraction over nucleophilic addition.