Influence of Ligand Architecture on Oxidation Reactions by High‐Valent Nonheme Manganese Oxo Complexes Using Water as a Source of Oxygen |
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| Authors: | Prasenjit Barman Dr Anil Kumar Vardhaman Dr Bodo Martin Svenja J Wörner Dr Chivukula V Sastri Prof Dr Peter Comba |
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| Affiliation: | 1. Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 (India);2. Anorganisch‐Chemisches Institut and Interdisciplinary Center for Scientific Computing (IWR), Universit?t Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg (Germany) |
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| Abstract: | Mononuclear nonheme MnIV?O complexes with two isomers of a bispidine ligand have been synthesized and characterized by various spectroscopies and density functional theory (DFT). The MnIV?O complexes show reactivity in oxidation reactions (hydrogen‐atom abstraction and sulfoxidation). Interestingly, one of the isomers (L1) is significantly more reactive than the other (L2), while in the corresponding FeIV?O based oxidation reactions the L2‐based system was previously found to be more reactive than the L1‐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. |
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| Keywords: | density functional calculations isomers manganese oxidation structure elucidation |
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