English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  Mononuclear Manganese(III) Superoxo Complexes: Synthesis, Characterization, and Reactivity

Lin, Y.-H., Cramer, H. H., van Gastel, M., Tsai, Y.-H., Chu, C.-Y., Kuo, T.-S., et al. (2019). Mononuclear Manganese(III) Superoxo Complexes: Synthesis, Characterization, and Reactivity. Inorganic Chemistry, 58(15), 9756-9765. doi:10.1021/acs.inorgchem.9b00767.

Item is

Basic

show hide
Genre: Journal Article

Files

show Files

Locators

show

Creators

show
hide
 Creators:
Lin, Yen-Hao1, Author
Cramer, Hanna Hinrika2, Author
van Gastel, Maurice3, Author           
Tsai, Yi-Hsuan1, Author
Chu, Chi-Yi1, Author
Kuo, Ting-Shen4, Author
Lee, I-Ren1, Author
Ye, Shengfa5, Author           
Bill, Eckhard2, Author
Lee, Way-Zen1, 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              
4Instrumentation Center, Department of Chemistry, National Taiwan Normal University, Taipei 11677, Taiwan, ou_persistent22              
5Research Group Ye, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541708              

Content

show
hide
Free keywords: -
 Abstract: Metal–superoxo species are typically proposed as key intermediates in the catalytic cycle of dioxygen activation by metalloenzymes involving different transition metal cofactors. In this regard, while a series of Fe–, Co–, and Ni–superoxo complexes have been reported to date, well-defined Mn–superoxo complexes remain rather rare. Herein, we report two mononuclear MnIII–superoxo species, Mn(BDPP)(O2•–) (2, H2BDPP = 2,6-bis((2-(S)-diphenylhydroxylmethyl-1-pyrrolidinyl)methyl)pyridine) and Mn(BDPBrP)(O2•–) (2′, H2BDPBrP = 2,6-bis((2-(S)-di(4-bromo)phenylhydroxyl-methyl-1-pyrrolidinyl)methyl)pyridine), synthesized by bubbling O2 into solutions of their MnII precursors, Mn(BDPP) (1) and Mn(BDPBrP) (1′), at −80 °C. A combined spectroscopic (resonance Raman and electron paramagnetic resonance (EPR) spectroscopy) and computational study evidence that both complexes contain a high-spin MnIII center (SMn = 2) antiferromagnetically coupled to a superoxo radical ligand (SOO• = 1/2), yielding an overall S = 3/2 ground state. Complexes 2 and 2′ were shown to be capable of abstracting a H atom from 2,2,6,6-tetramethyl-1-hydroxypiperidine (TEMPO-H) to form MnIII–hydroperoxo species, Mn(BDPP)(OOH) (5) and Mn(BDPBrP)(OOH) (5′). Complexes 5 and 5′ can be independently prepared by the reactions of the isolated MnIII-aqua complexes, [Mn(BDPP)(H2O)]OTf (6) and [Mn(BDPBrP)(H2O)]OTf (6′), with H2O2 in the presence of NEt3. The parallel-mode EPR measurements established a high-spin S = 2 ground state for 5 and 5′.

Details

show
hide
Language(s): eng - English
 Dates: 2019-03-182019-07-222019-08-05
 Publication Status: Published in print
 Pages: 10
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.inorgchem.9b00767
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 58 (15) Sequence Number: - Start / End Page: 9756 - 9765 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669