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Synthesis and Characterization of a Dinuclear Manganese(III,III) Complex with Three Phenolate Ligands

Lomoth, Reiner; Huang, Ping LU ; Zheng, Jiutian; Sun, Licheng; Hammarström, Leif; Åkermark, Björn and Styring, Stenbjörn LU (2002) In European Journal of Inorganic Chemistry 2002(11). p.2965-2974
Abstract
A dinuclear manganese complex ([Mn2L(m-OAc)2]PF6) has been synthesized, where L is the trianion of 2,6-bis{[(2-hydroxy-3,5-di-tert-butylbenzyl)(2-pyridylmethyl)amino]methyl}-4-methylphenol, a ligand with three phenolate groups. The two pseudo-octahedrally coordinated Mn ions are bridged via the two bidentate acetate ligands and the 4-methylphenolate group of the ligand. We have characterized the complex with electrochemistry, spectroelectrochemistry and EPR spectroscopy. Electrochemically the Mn2III,III complex undergoes two metal-centered quasi-reversible one-electron reduction steps (E1/2 = 0.04 and -0.32 V vs. SCE). Reduction to the Mn2II,III state results in transformation into a modified complex with slightly different redox... (More)
A dinuclear manganese complex ([Mn2L(m-OAc)2]PF6) has been synthesized, where L is the trianion of 2,6-bis{[(2-hydroxy-3,5-di-tert-butylbenzyl)(2-pyridylmethyl)amino]methyl}-4-methylphenol, a ligand with three phenolate groups. The two pseudo-octahedrally coordinated Mn ions are bridged via the two bidentate acetate ligands and the 4-methylphenolate group of the ligand. We have characterized the complex with electrochemistry, spectroelectrochemistry and EPR spectroscopy. Electrochemically the Mn2III,III complex undergoes two metal-centered quasi-reversible one-electron reduction steps (E1/2 = 0.04 and -0.32 V vs. SCE). Reduction to the Mn2II,III state results in transformation into a modified complex with slightly different redox properties. One-electron oxidation (E1/2 = 0.96 V vs. SCE) affords the Mn2III,IV state while further one-electron oxidation (E1/2 = 1.13 V vs. SCE) presumably involves ligand oxidation. High valent Mn complexes involving MnIV or MnV centers are of particular interest as intermediates in catalytic water oxidation. The redox potentials of [Mn2L(m-OAc)2]+ show the expected stabilization of higher manganese oxidation states compared with the related complex, [Mn2(bpmp)(m-OAc)2]+. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002) (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Manganese, Ligand design, Redox chemistry
in
European Journal of Inorganic Chemistry
volume
2002
issue
11
pages
2965 - 2974
publisher
John Wiley & Sons
external identifiers
  • wos:000178876500029
  • scopus:0036840961
ISSN
1099-0682
DOI
10.1002/1099-0682(200211)2002:11<2965::AID-EJIC2965>3.0.CO;2-3
language
English
LU publication?
yes
id
180b4f19-b0aa-44e3-a96e-aeccafd4ff22 (old id 124819)
date added to LUP
2007-07-06 09:58:32
date last changed
2017-12-10 03:42:23
@article{180b4f19-b0aa-44e3-a96e-aeccafd4ff22,
  abstract     = {A dinuclear manganese complex ([Mn2L(m-OAc)2]PF6) has been synthesized, where L is the trianion of 2,6-bis{[(2-hydroxy-3,5-di-tert-butylbenzyl)(2-pyridylmethyl)amino]methyl}-4-methylphenol, a ligand with three phenolate groups. The two pseudo-octahedrally coordinated Mn ions are bridged via the two bidentate acetate ligands and the 4-methylphenolate group of the ligand. We have characterized the complex with electrochemistry, spectroelectrochemistry and EPR spectroscopy. Electrochemically the Mn2III,III complex undergoes two metal-centered quasi-reversible one-electron reduction steps (E1/2 = 0.04 and -0.32 V vs. SCE). Reduction to the Mn2II,III state results in transformation into a modified complex with slightly different redox properties. One-electron oxidation (E1/2 = 0.96 V vs. SCE) affords the Mn2III,IV state while further one-electron oxidation (E1/2 = 1.13 V vs. SCE) presumably involves ligand oxidation. High valent Mn complexes involving MnIV or MnV centers are of particular interest as intermediates in catalytic water oxidation. The redox potentials of [Mn2L(m-OAc)2]+ show the expected stabilization of higher manganese oxidation states compared with the related complex, [Mn2(bpmp)(m-OAc)2]+. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)},
  author       = {Lomoth, Reiner and Huang, Ping and Zheng, Jiutian and Sun, Licheng and Hammarström, Leif and Åkermark, Björn and Styring, Stenbjörn},
  issn         = {1099-0682},
  keyword      = {Manganese,Ligand design,Redox chemistry},
  language     = {eng},
  number       = {11},
  pages        = {2965--2974},
  publisher    = {John Wiley & Sons},
  series       = {European Journal of Inorganic Chemistry},
  title        = {Synthesis and Characterization of a Dinuclear Manganese(III,III) Complex with Three Phenolate Ligands},
  url          = {http://dx.doi.org/10.1002/1099-0682(200211)2002:11<2965::AID-EJIC2965>3.0.CO;2-3},
  volume       = {2002},
  year         = {2002},
}