Influence of ligand architecture on oxidation reactions by high-valent nonheme manganese oxo complexes using water as a source of oxygen
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,...
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| Main Authors: | , , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
2015
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| In: |
Angewandte Chemie. International edition
Year: 2014, Volume: 54, Issue: 7, Pages: 2095-2099 |
| ISSN: | 1521-3773 |
| DOI: | 10.1002/anie.201409476 |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1002/anie.201409476 Verlag, lizenzpflichtig, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201409476 
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| Author Notes: | Prasenjit Barman, Anil Kumar Vardhaman, Bodo Martin, Svenja J. Wörner, Chivukula V. Sastri, and Peter Comba |
| Summary: | 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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| Item Description: | First published: 29 December 2014 Gesehen am 30.07.2020 |
| Physical Description: | Online Resource |
| ISSN: | 1521-3773 |
| DOI: | 10.1002/anie.201409476 |