Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 24, Issue 68, Pages 17927-17931Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201804898
Keywords
C-H bond activation; manganese; olefin epoxidation; radicals; sulfoxidation
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Funding
- NRF of Korea [NRF-2012R1A3A2048842, NRF-2010-00353, NRF-2017R1C1B2002037]
- Sookmyung Women's University Grants [1-1603-2053]
- NIH National Institute of General Medical Sciences (NIGMS) through a Biomedical Technology Research Resource P41 grant [P41GM103393]
- DOE Office of Biological and Environmental Research
- NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES [P41GM103393] Funding Source: NIH RePORTER
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A mononuclear manganese(V)-oxo complex with tetraamido macrocyclic ligand (TAML), [Mn-V(O)(TAML)](-) (1), is a sluggish oxidant in oxidation reactions. Herein, a mononuclear manganese(V)-oxo TAML cation radical complex, [Mn-V(O)(TAML(+.))] (2), is reported. It was synthesized by reacting [Mn-III(TAML)](-) with 3.0 equivalents of [Ru-III(bpy)(3)](3+) or upon addition of one-electron oxidant to 1 and then characterized thoroughly with various spectroscopic techniques along with DFT calculations. Although 1 is a sluggish oxidant, 2 is a strong oxidant capable of activating C-H bonds of hydrocarbons (i.e., hydrogen atom transfer reaction) and transferring its oxygen atom to thioanisoles and olefins (i.e., oxygen atom transfer reaction).
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