Deformylation Reaction by a Nonheme Manganese(III)–Peroxo Complex via Initial Hydrogen-Atom Abstraction
Prasenjit Barman
Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 India
Search for more papers by this authorPranav Upadhyay
Department of Applied Physics, School of Physical Sciences, Babasaheb Bhimrao Ambedkar University, Lucknow, 226025 India
Search for more papers by this authorAbayomi S. Faponle
Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science, The University of Manchester, 131 Princess Street, Manchester, M1 7DN UK
Search for more papers by this authorJitendra Kumar
Department of Applied Physics, School of Physical Sciences, Babasaheb Bhimrao Ambedkar University, Lucknow, 226025 India
Search for more papers by this authorSayanta Sekhar Nag
Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 India
Search for more papers by this authorCorresponding Author
Dr. Devesh Kumar
Department of Applied Physics, School of Physical Sciences, Babasaheb Bhimrao Ambedkar University, Lucknow, 226025 India
Search for more papers by this authorCorresponding Author
Dr. Chivukula V. Sastri
Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 India
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Dr. Sam P. de Visser
Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science, The University of Manchester, 131 Princess Street, Manchester, M1 7DN UK
Search for more papers by this authorPrasenjit Barman
Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 India
Search for more papers by this authorPranav Upadhyay
Department of Applied Physics, School of Physical Sciences, Babasaheb Bhimrao Ambedkar University, Lucknow, 226025 India
Search for more papers by this authorAbayomi S. Faponle
Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science, The University of Manchester, 131 Princess Street, Manchester, M1 7DN UK
Search for more papers by this authorJitendra Kumar
Department of Applied Physics, School of Physical Sciences, Babasaheb Bhimrao Ambedkar University, Lucknow, 226025 India
Search for more papers by this authorSayanta Sekhar Nag
Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 India
Search for more papers by this authorCorresponding Author
Dr. Devesh Kumar
Department of Applied Physics, School of Physical Sciences, Babasaheb Bhimrao Ambedkar University, Lucknow, 226025 India
Search for more papers by this authorCorresponding Author
Dr. Chivukula V. Sastri
Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 India
Search for more papers by this authorCorresponding Author
Dr. Sam P. de Visser
Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science, The University of Manchester, 131 Princess Street, Manchester, M1 7DN UK
Search for more papers by this authorAbstract
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.
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