Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 140, Issue 47, Pages 16037-16041Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b10244
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Funding
- NRF [2017R1A2B4005441]
- Ministry of Science, ICT and Future Planning of Korea [CGRC 2016M3D3A01913243]
- Ministry of Science, ICT and Future Planning (DGIST R&D Program) of Korea [19-BD-0403]
- Ministry of Education, Culture, Sports, Science and Technology of Japan [15H00960]
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Transition metal-iodosylarene complexes have been proposed to be key intermediates in the catalytic cycles of metal catalysts with iodosylarene. We report the first X-ray crystal structure and spectroscopic characterization of a mononuclear nonheme manganese-(III)-iodosylarene complex with a tetradentate macro cyclic ligand, [Mn-III(TBDAP)(OIPh)(OH)](2+) (2). The manganese(III) iodosylarene complex is capable of conducting various oxidation reactions with organic substrates, such as C-H bond activation, sulfoxidation and epoxidation. Kinetic studies including isotope labeling experiments and Hammett correlation demonstrate the electrophilic character on the Mn-iodosylarene adduct. This novel intermediate would be prominently valuable for expanding the chemistry of transition metal catalysts.
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