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- Title
Influence of Ligand Architecture on Oxidation Reactions by High-Valent Nonheme Manganese Oxo Complexes Using Water as a Source of Oxygen.
- Authors
Barman, Prasenjit; Vardhaman, Anil Kumar; Sastri, Chivukula V.; Martin, Bodo; Wörner, Svenja J.; Comba, Peter
- 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.
- Subjects
MOLECULAR structure of ligands; DENSITY functional theory; OXO compounds; OXYGEN in water; OXYGEN-evolving complex (Photosynthesis); VALENCE (Chemistry)
- Publication
Angewandte Chemie International Edition, 2015, Vol 54, Issue 7, p2095
- ISSN
1433-7851
- Publication type
Article
- DOI
10.1002/anie.201409476