English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  A Manganese(IV)-Hydroperoxo Intermediate Generated by Protonation of the Corresponding Manganese(III)-Superoxo Complex

Lin, Y.-H., Kutin, Y., van Gastel, M., Bill, E., Schnegg, A., Ye, S., et al. (2020). A Manganese(IV)-Hydroperoxo Intermediate Generated by Protonation of the Corresponding Manganese(III)-Superoxo Complex. Journal of the American Chemical Society, 142(33), 10255-10260. doi:10.1021/jacs.0c02756.

Item is

Basic

show hide
Genre: Journal Article

Files

show Files

Locators

show

Creators

show
hide
 Creators:
Lin, Yen-Hao1, Author
Kutin, Yuri2, Author
van Gastel, Maurice3, Author           
Bill, Eckhard2, Author
Schnegg, Alexander2, Author
Ye, Shengfa4, 5, Author           
Lee, Way-Zen1, 6, Author
Affiliations:
1Department of Chemistry, National Taiwan Normal University, Taipei 11677, Taiwan, ou_persistent22              
2Max-Planck-Institut für Chemische Energiekonversion, Mülheim an der Ruhr D-45470, Germany, ou_persistent22              
3Research Group van Gastel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541713              
4State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China, ou_persistent22              
5Research Group Ye, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541708              
6Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 807, Taiwan, ou_persistent22              

Content

show
hide
Free keywords: -
 Abstract: Earlier work revealed that metal-superoxo species primarily function as radicals and/or electrophiles. Herein, we present ambiphilicity of a MnIII-superoxo complex revealed by its proton- and metal-coupled electron-transfer processes. Specifically, a MnIV-hydroperoxo intermediate, [Mn(BDPBrP)(OOH)]+ (1, H2BDPBrP = 2,6-bis((2-(S)-di(4-bromo)phenylhydroxylmethyl-1-pyrrolidinyl)methyl)pyridine) was generated by treatment of a MnIII-superoxo complex, Mn(BDPBrP)(O2) (2) with trifluoroacetic acid at −120 °C. Detailed insights into the electronic structure of 1 are obtained using resonance Raman and multi-frequency electron paramagnetic resonance spectroscopies coupled with density functional theory calculations. Similarly, the reaction of 2 with scandium(III) triflate was shown to give a Mn(IV)/Sc(III) bridging peroxo species, [Mn(BDPBrP)(OO)Sc(OTf)n](3-n)+ (4). Furthermore, it is found that deprotonation of 1 quantitatively regenerates 2, and that one-electron oxidation of the corresponding MnIII-hydroperoxo species, Mn(BDPBrP)(OOH) (3), also yields 1.

Details

show
hide
Language(s): eng - English
 Dates: 2020-03-122020-05-152020-06-10
 Publication Status: Published in print
 Pages: 6
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.0c02756
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 142 (33) Sequence Number: - Start / End Page: 10255 - 10260 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870