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Influence of Ligand Architecture on Oxidation Reactions by High‐Valent Nonheme Manganese Oxo Complexes Using Water as a Source of Oxygen
Author(s) -
Barman Prasenjit,
Vardhaman Anil Kumar,
Martin Bodo,
Wörner Svenja J.,
Sastri Chivukula V.,
Comba Peter
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201409476
Subject(s) - chemistry , steric effects , manganese , reactivity (psychology) , density functional theory , ligand (biochemistry) , catalysis , hydrogen atom abstraction , redox , photochemistry , computational chemistry , hydrogen , stereochemistry , inorganic chemistry , organic chemistry , medicine , biochemistry , alternative medicine , receptor , pathology
Mononuclear nonheme Mn IV O complexes with two isomers of a bispidine ligand have been synthesized and characterized by various spectroscopies and density functional theory (DFT). The Mn IV O complexes show reactivity in oxidation reactions (hydrogen‐atom abstraction and sulfoxidation). Interestingly, one of the isomers (L 1 ) is significantly more reactive than the other (L 2 ), while in the corresponding Fe IV O based oxidation reactions the L 2 ‐based system was previously found to be more reactive than the L 1 ‐based catalyst. This inversion of reactivities is discussed on the basis of DFT and molecular mechanics (MM) model calculations, which indicate that the order of reactivities are primarily due to a switch of reaction channels (σ versus π) and concomitant steric effects.