title: Deformylation Reaction by a Nonheme Manganese(III)-Peroxo Complex via Initial Hydrogen-Atom Abstraction.
abstract: 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.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039, India.
authors.forename: Prasenjit
authors.identifier: 0000-0002-4409-2782
authors.initials: P
authors.lastname: Barman
authors.affiliation: Department of Applied Physics, School of Physical Sciences, Babasaheb Bhimrao Ambedkar University, Lucknow, 226025, India.
authors.forename: Pranav
authors.identifier: 0000-0002-6151-1213
authors.initials: P
authors.lastname: Upadhyay
authors.affiliation: Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science, The University of Manchester, 131 Princess Street, Manchester, M1 7DN, UK.
authors.forename: Abayomi S
authors.identifier: 0000-0002-6989-0342
authors.initials: AS
authors.lastname: Faponle
authors.affiliation: Department of Applied Physics, School of Physical Sciences, Babasaheb Bhimrao Ambedkar University, Lucknow, 226025, India.
authors.forename: Jitendra
authors.identifier: 0000-0002-3721-4147
authors.initials: J
authors.lastname: Kumar
authors.affiliation: Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039, India.
authors.forename: Sayanta Sekhar
authors.identifier: 0000-0003-0945-9507
authors.initials: SS
authors.lastname: Nag
authors.affiliation: Department of Applied Physics, School of Physical Sciences, Babasaheb Bhimrao Ambedkar University, Lucknow, 226025, India. dkclcre@yahoo.com.
authors.forename: Devesh
authors.identifier: 0000-0001-5867-1905
authors.initials: D
authors.lastname: Kumar
authors.affiliation: Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039, India. sastricv@iitg.ernet.in.
authors.forename: Chivukula V
authors.identifier: 0000-0003-0477-7741
authors.initials: CV
authors.lastname: Sastri
authors.affiliation: Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science, The University of Manchester, 131 Princess Street, Manchester, M1 7DN, UK. sam.devisser@manchester.ac.uk.
authors.forename: Sam P
authors.identifier: 0000-0002-2620-8788
authors.initials: SP
authors.lastname: de Visser
keywords: biomimetic models; density functional theory; enzyme models; hydrogen-atom abstraction; reaction mechanisms