Influence of Ligand Architecture on Oxidation Reactions by High-Valent Nonheme Manganese Oxo Complexes Using Water as a Source of Oxygen†
Prasenjit Barman
Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 (India)
Search for more papers by this authorDr. Anil Kumar Vardhaman
Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 (India)
Search for more papers by this authorDr. Bodo Martin
Anorganisch-Chemisches Institut and Interdisciplinary Center for Scientific Computing (IWR), Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg (Germany)
Search for more papers by this authorSvenja J. Wörner
Anorganisch-Chemisches Institut and Interdisciplinary Center for Scientific Computing (IWR), Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg (Germany)
Search for more papers by this authorCorresponding Author
Dr. Chivukula V. Sastri
Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 (India)
Chivukula V. Sastri, Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 (India)
Peter Comba, Anorganisch-Chemisches Institut and Interdisciplinary Center for Scientific Computing (IWR), Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg (Germany)
Search for more papers by this authorCorresponding Author
Prof. Dr. Peter Comba
Anorganisch-Chemisches Institut and Interdisciplinary Center for Scientific Computing (IWR), Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg (Germany)
Chivukula V. Sastri, Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 (India)
Peter Comba, Anorganisch-Chemisches Institut and Interdisciplinary Center for Scientific Computing (IWR), Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg (Germany)
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 authorDr. Anil Kumar Vardhaman
Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 (India)
Search for more papers by this authorDr. Bodo Martin
Anorganisch-Chemisches Institut and Interdisciplinary Center for Scientific Computing (IWR), Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg (Germany)
Search for more papers by this authorSvenja J. Wörner
Anorganisch-Chemisches Institut and Interdisciplinary Center for Scientific Computing (IWR), Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg (Germany)
Search for more papers by this authorCorresponding Author
Dr. Chivukula V. Sastri
Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 (India)
Chivukula V. Sastri, Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 (India)
Peter Comba, Anorganisch-Chemisches Institut and Interdisciplinary Center for Scientific Computing (IWR), Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg (Germany)
Search for more papers by this authorCorresponding Author
Prof. Dr. Peter Comba
Anorganisch-Chemisches Institut and Interdisciplinary Center for Scientific Computing (IWR), Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg (Germany)
Chivukula V. Sastri, Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 (India)
Peter Comba, Anorganisch-Chemisches Institut and Interdisciplinary Center for Scientific Computing (IWR), Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg (Germany)
Search for more papers by this authorResearch support was provided by the Department of Science and Technology, India (SR/S1/IC-02/2009) and the Council for Scientific & Industrial Research (01(2527)/11/EMR-II) to C.V.S. Support by the University of Heidelberg is gratefully acknowledged.
Abstract
Mononuclear nonheme MnIVO complexes with two isomers of a bispidine ligand have been synthesized and characterized by various spectroscopies and density functional theory (DFT). The MnIVO 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 FeIVO 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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