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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

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,...

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Hauptverfasser: Barman, Prasenjit (VerfasserIn) , Vardhaman, Anil Kumar (VerfasserIn) , Martin, Bodo (VerfasserIn) , Wörner, Svenja (VerfasserIn) , Sastri, Chivukula V. (VerfasserIn) , Comba, Peter (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: 2015
In: Angewandte Chemie. International edition
Year: 2014, Jahrgang: 54, Heft: 7, Pages: 2095-2099
ISSN:1521-3773
DOI:10.1002/anie.201409476
Online-Zugang:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1002/anie.201409476
Verlag, lizenzpflichtig, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201409476
Volltext
Verfasserangaben:Prasenjit Barman, Anil Kumar Vardhaman, Bodo Martin, Svenja J. Wörner, Chivukula V. Sastri, and Peter Comba
Beschreibung
Zusammenfassung: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.
Beschreibung:First published: 29 December 2014
Gesehen am 30.07.2020
Beschreibung:Online Resource
ISSN:1521-3773
DOI:10.1002/anie.201409476

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