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Generation of a Mn(IV)-Peroxo or Mn(III)-Oxo-Mn(III) Species upon Oxygenation of Mono- and Binuclear Thiolate-Ligated Mn(II) Complexes

A thiolate-bridged binuclear complex [PPN][(Mn(PS3))] (1, PPN = bis(triphenylphosphine)iminium and PS3H = (2,2',2″-trimercapto-3,3',3″-tris(trimethylsilyl)triphenylphosphine)), prepared from the reaction of MnCl/[PPN]Cl and Li[PS3], converts into a mononuclear complex [PPN][Mn(PS3)(DABCO)] (2) in th... Full description

Journal Title: Inorganic chemistry 05 September 2017, Vol.56(17), pp.10559-10569
Main Author: Lee, Chien-Ming
Other Authors: Wu, Wun-Yan , Chiang, Ming-Hsi , Bohle, D Scott , Lee, Gene-Hsiang
Format: Electronic Article Electronic Article
Language: English
Subjects:
ID: E-ISSN: 1520-510X ; PMID: 28825825 Version:1 ; DOI: 10.1021/acs.inorgchem.7b01513
Link: http://pubmed.gov/28825825
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recordid: medline28825825
title: Generation of a Mn(IV)-Peroxo or Mn(III)-Oxo-Mn(III) Species upon Oxygenation of Mono- and Binuclear Thiolate-Ligated Mn(II) Complexes
format: Article
creator:
  • Lee, Chien-Ming
  • Wu, Wun-Yan
  • Chiang, Ming-Hsi
  • Bohle, D Scott
  • Lee, Gene-Hsiang
subjects:
  • Chemistry
ispartof: Inorganic chemistry, 05 September 2017, Vol.56(17), pp.10559-10569
description: A thiolate-bridged binuclear complex [PPN][(Mn(PS3))] (1, PPN = bis(triphenylphosphine)iminium and PS3H = (2,2',2″-trimercapto-3,3',3″-tris(trimethylsilyl)triphenylphosphine)), prepared from the reaction of MnCl/[PPN]Cl and Li[PS3], converts into a mononuclear complex [PPN][Mn(PS3)(DABCO)] (2) in the presence of excess amounts of DABCO (DABCO = 1,4-diazabicyclo[2.2.2]octane). Variable temperature studies of solution containing 1 and DABCO by UV-vis spectroscopy indicate that 1 and 2 exist in significant amounts in equilibrium and mononuclear 2 is favored at low temperature. Treatment of 1 or 2 with the monomeric O-side-on-bound [PPN][Mn(O)(PS3)] (3) produces the mono-oxo-bridged dimer [PPN][(Mn(PS3))(μ-O)] (4). The electrochemistry of 1 and 2 reveals anodic peak(s) for a MnMn redox couple at shifted potentials against Fc/Fc, indicating that both complexes can be oxidized by dioxygen. The O activation mediated by 1 and 2 is investigated in both solution and the solid state. Microcrystals...
language: eng
source:
identifier: E-ISSN: 1520-510X ; PMID: 28825825 Version:1 ; DOI: 10.1021/acs.inorgchem.7b01513
fulltext: fulltext
issn:
  • 1520510X
  • 1520-510X
url: Link


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titleGeneration of a Mn(IV)-Peroxo or Mn(III)-Oxo-Mn(III) Species upon Oxygenation of Mono- and Binuclear Thiolate-Ligated Mn(II) Complexes
creatorLee, Chien-Ming ; Wu, Wun-Yan ; Chiang, Ming-Hsi ; Bohle, D Scott ; Lee, Gene-Hsiang
ispartofInorganic chemistry, 05 September 2017, Vol.56(17), pp.10559-10569
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descriptionA thiolate-bridged binuclear complex [PPN][(Mn(PS3))] (1, PPN = bis(triphenylphosphine)iminium and PS3H = (2,2',2″-trimercapto-3,3',3″-tris(trimethylsilyl)triphenylphosphine)), prepared from the reaction of MnCl/[PPN]Cl and Li[PS3], converts into a mononuclear complex [PPN][Mn(PS3)(DABCO)] (2) in the presence of excess amounts of DABCO (DABCO = 1,4-diazabicyclo[2.2.2]octane). Variable temperature studies of solution containing 1 and DABCO by UV-vis spectroscopy indicate that 1 and 2 exist in significant amounts in equilibrium and mononuclear 2 is favored at low temperature. Treatment of 1 or 2 with the monomeric O-side-on-bound [PPN][Mn(O)(PS3)] (3) produces the mono-oxo-bridged dimer [PPN][(Mn(PS3))(μ-O)] (4). The electrochemistry of 1 and 2 reveals anodic peak(s) for a MnMn redox couple at shifted potentials against Fc/Fc, indicating that both complexes can be oxidized by dioxygen. The O activation mediated by 1 and 2 is investigated in both solution and the solid state. Microcrystals...
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titleGeneration of a Mn(IV)-Peroxo or Mn(III)-Oxo-Mn(III) Species upon Oxygenation of Mono- and Binuclear Thiolate-Ligated Mn(II) Complexes
descriptionA thiolate-bridged binuclear complex [PPN][(Mn(PS3))] (1, PPN = bis(triphenylphosphine)iminium and PS3H = (2,2',2″-trimercapto-3,3',3″-tris(trimethylsilyl)triphenylphosphine)), prepared from the reaction of MnCl/[PPN]Cl and Li[PS3], converts into a mononuclear complex [PPN][Mn(PS3)(DABCO)] (2) in the presence of excess amounts of DABCO (DABCO = 1,4-diazabicyclo[2.2.2]octane). Variable temperature studies of solution containing 1 and DABCO by UV-vis spectroscopy indicate that 1 and 2 exist in significant amounts in equilibrium and mononuclear 2 is favored at low temperature. Treatment of 1 or 2 with the monomeric O-side-on-bound [PPN][Mn(O)(PS3)] (3) produces the mono-oxo-bridged dimer [PPN][(Mn(PS3))(μ-O)] (4). The electrochemistry of 1 and 2 reveals anodic peak(s) for a MnMn redox couple at shifted potentials against Fc/Fc, indicating that both complexes can be oxidized by dioxygen. The O activation mediated by 1 and 2 is investigated in both solution and the solid state. Microcrystals...
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abstractA thiolate-bridged binuclear complex [PPN][(Mn(PS3))] (1, PPN = bis(triphenylphosphine)iminium and PS3H = (2,2',2″-trimercapto-3,3',3″-tris(trimethylsilyl)triphenylphosphine)), prepared from the reaction of MnCl/[PPN]Cl and Li[PS3], converts into a mononuclear complex [PPN][Mn(PS3)(DABCO)] (2) in the presence of excess amounts of DABCO (DABCO = 1,4-diazabicyclo[2.2.2]octane). Variable temperature studies of solution containing 1 and DABCO by UV-vis spectroscopy indicate that 1 and 2 exist in significant amounts in equilibrium and mononuclear 2 is favored at low temperature. Treatment of 1 or 2 with the monomeric O-side-on-bound [PPN][Mn(O)(PS3)] (3) produces the mono-oxo-bridged dimer [PPN][(Mn(PS3))(μ-O)] (4). The electrochemistry of 1 and 2 reveals anodic peak(s) for a MnMn redox couple at shifted potentials against Fc/Fc, indicating that both complexes can be oxidized by dioxygen. The O activation mediated by 1 and 2 is investigated in both solution and the solid state. Microcrystals...
doi10.1021/acs.inorgchem.7b01513
pmid28825825
orcidid0000-0001-8529-4279
date2017-09-05