A Mechanistic Spectrum of O-H Bond Cleavage Observed for Reactions of Phenols with a Manganese Superoxo Complex.

Autor: Tian YC; Department of Chemistry, National Taiwan Normal University, 11677, Taipei, Taiwan., Zhang P; State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 116023, Dalian, China.; University of Chinese Academy of Sciences, 100049, Beijing, China., Lin KT; Department of Chemistry, National Taiwan Normal University, 11677, Taipei, Taiwan., Fu CW; Department of Chemistry, National Taiwan Normal University, 11677, Taipei, Taiwan., Ye S; State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 116023, Dalian, China., Lee WZ; Department of Chemistry, National Taiwan Normal University, 11677, Taipei, Taiwan.; Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, 807, Kaohsiung, Taiwan.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Jul 16; Vol. 30 (40), pp. e202401826. Date of Electronic Publication: 2024 May 29.
DOI: 10.1002/chem.202401826
Abstrakt: Reaction of a rare and well-characterized Mn III -superoxo species, Mn(BDP Br P)(O 2 ⋅) (1, H 2 BDP Br P=2,6-bis((2-(S)-di(4-bromo)phenylhydroxylmethyl-1-pyrrolidinyl)methyl)pyridine), with 4-dimethylaminophenol at -80 °C proceeds via concerted proton electron transfer (CPET) to produce a Mn III -hydroperoxo complex, Mn(BDP Br P)(OOH) (2), alongside 4-dimethylaminophenoxy radical; whereas, upon treatment with 4-nitrophenol, complex 1 undergoes a proton transfer process to afford a Mn IV -hydroperoxo complex, [Mn(BDP Br P)(OOH)] + (3). Intriguingly, the reactions of 1 with 4-chlorophenol and 4-methoxyphenol follow two routes of CPET and sequential proton and electron transfer to furnish complex 2 in the end. UV-vis and EPR spectroscopic studies coupled with DFT calculations provided support for this wide mechanistic spectrum of activating various phenol O-H bonds by a single Mn III -superoxo complex, 1.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
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