期刊
FRONTIERS IN CHEMISTRY
卷 8, 期 -, 页码 -出版社
FRONTIERS MEDIA SA
DOI: 10.3389/fchem.2020.00744
关键词
manganese(III)-iodosylarene; sulfoxidation; C-H bond activation; mechanism; DFT
资金
- National Natural Science Foundation of China [21873052]
- Natural Science Foundation of Zhejiang Province [LQ20B030004]
- open fund of the State Key Laboratory of Molecular Reaction Dynamics [SKLMRD-K202005]
Metal-iodosylarene complexes have been recently viewed as a second oxidant alongside of the well-known high-valent metal-oxo species. Extensive efforts have been exerted to unveil the structure-function relationship of various metal-iodosylarene complexes. In the present manuscript, density functional theoretical calculations were employed to investigate such relationship of a specific manganese-iodosylbenzene complex [Mn-III(TBDAP)(PhIO)(OH)](2+)(1). Our results fit the experimental observations and revealed new mechanistic findings.1acts as a stepwise 1e+1e oxidant in sulfoxidation reactions. Surprisingly, C-H bond activation of 9,10-dihydroanthracene (DHA) by1proceeds via a novel ionic hydride transfer/proton transfer (HT/PT) mechanism. As a comparison to1, the electrophilicity of an iodosylbenzene monomer PhIO was investigated. PhIO performs concerted 2e-oxidations both in sulfoxidation and C-H activation. Hydroxylation of DHA by PhIO was found to proceed via a novel ionic and concerted proton-transfer/hydroxyl-rebound mechanism involving 2e-oxidation to form a transient carbonium species.
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