Models for the photosynthetic water oxidizing enzyme. 2. Electronic, magnetic, and EPR characterization of a binuclear manganese(II) semiquinone complex

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Abstract

The preparation and characterization of a tetranuclear manganese complex, Mn4(ASQ)4(CO)8, and a binuclear complex into which it dissociates in solution, Mn2(ASQ)4L2 (ASQ = 2-acetyl-1,4-benzosemiquinone), is described. EPR spectroscopy and variable temperature magnetic susceptibility of the solution species indicate that there are two equivalent Mn(II) ions coupled by a ferromagnetic exchange interaction, having J ≥ 23 cm-1, fostered by two bridging semiquinones. This is evidenced by a paramagnetic ground state with a magnetic moment μeff = 6.78, electron spin resonance fine structure consistent with an apparent spin S = 3 and having zero-field splitting parameters of \D\ = 0.103 cm-1 and |E| = 0.011 cm-1, a nearly isotropic 11-line hyperfine structure for 55Mn with coupling constant \A\ = 45 ± 3 G, and a nearly isotropci g = 2. The quenching of the magnetic moment of the dimer with increasing temperature is interpreted to arise from the ferromagnetic coupling and, near room temperature, from an internal redox equilibrium in which Mn2(AQL)4L2 and possibly Mn2-(ASQ)2(AQL)2L2 (AQL = 2-acetyl-1,4-benzoquinol dianion) form. This complex is discussed in relation to its suitability as a model for the magnetic properties of the photosynthetic water-oxidizing enzyme.

Original languageEnglish
Pages (from-to)7093-7098
Number of pages6
JournalJournal of the American Chemical Society
Volume105
Issue number24
Publication statusPublished - 1983

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Manganese
Paramagnetic resonance
Enzymes
Magnetic moments
Temperature
Water
Exchange interactions
Electron Spin Resonance Spectroscopy
Carbon Monoxide
Magnetic susceptibility
Dimers
Ground state
Oxidation-Reduction
Quenching
Spectrum Analysis
Magnetic properties
Spectroscopy
Ions

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Models for the photosynthetic water oxidizing enzyme. 2. Electronic, magnetic, and EPR characterization of a binuclear manganese(II) semiquinone complex",
abstract = "The preparation and characterization of a tetranuclear manganese complex, Mn4(ASQ)4(CO)8, and a binuclear complex into which it dissociates in solution, Mn2(ASQ)4L2 (ASQ = 2-acetyl-1,4-benzosemiquinone), is described. EPR spectroscopy and variable temperature magnetic susceptibility of the solution species indicate that there are two equivalent Mn(II) ions coupled by a ferromagnetic exchange interaction, having J ≥ 23 cm-1, fostered by two bridging semiquinones. This is evidenced by a paramagnetic ground state with a magnetic moment μeff = 6.78, electron spin resonance fine structure consistent with an apparent spin S = 3 and having zero-field splitting parameters of \D\ = 0.103 cm-1 and |E| = 0.011 cm-1, a nearly isotropic 11-line hyperfine structure for 55Mn with coupling constant \A\ = 45 ± 3 G, and a nearly isotropci g = 2. The quenching of the magnetic moment of the dimer with increasing temperature is interpreted to arise from the ferromagnetic coupling and, near room temperature, from an internal redox equilibrium in which Mn2(AQL)4L2 and possibly Mn2-(ASQ)2(AQL)2L2 (AQL = 2-acetyl-1,4-benzoquinol dianion) form. This complex is discussed in relation to its suitability as a model for the magnetic properties of the photosynthetic water-oxidizing enzyme.",
author = "P. Mathur and Dismukes, {G Charles}",
year = "1983",
language = "English",
volume = "105",
pages = "7093--7098",
journal = "Journal of the American Chemical Society",
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T1 - Models for the photosynthetic water oxidizing enzyme. 2. Electronic, magnetic, and EPR characterization of a binuclear manganese(II) semiquinone complex

AU - Mathur, P.

AU - Dismukes, G Charles

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N2 - The preparation and characterization of a tetranuclear manganese complex, Mn4(ASQ)4(CO)8, and a binuclear complex into which it dissociates in solution, Mn2(ASQ)4L2 (ASQ = 2-acetyl-1,4-benzosemiquinone), is described. EPR spectroscopy and variable temperature magnetic susceptibility of the solution species indicate that there are two equivalent Mn(II) ions coupled by a ferromagnetic exchange interaction, having J ≥ 23 cm-1, fostered by two bridging semiquinones. This is evidenced by a paramagnetic ground state with a magnetic moment μeff = 6.78, electron spin resonance fine structure consistent with an apparent spin S = 3 and having zero-field splitting parameters of \D\ = 0.103 cm-1 and |E| = 0.011 cm-1, a nearly isotropic 11-line hyperfine structure for 55Mn with coupling constant \A\ = 45 ± 3 G, and a nearly isotropci g = 2. The quenching of the magnetic moment of the dimer with increasing temperature is interpreted to arise from the ferromagnetic coupling and, near room temperature, from an internal redox equilibrium in which Mn2(AQL)4L2 and possibly Mn2-(ASQ)2(AQL)2L2 (AQL = 2-acetyl-1,4-benzoquinol dianion) form. This complex is discussed in relation to its suitability as a model for the magnetic properties of the photosynthetic water-oxidizing enzyme.

AB - The preparation and characterization of a tetranuclear manganese complex, Mn4(ASQ)4(CO)8, and a binuclear complex into which it dissociates in solution, Mn2(ASQ)4L2 (ASQ = 2-acetyl-1,4-benzosemiquinone), is described. EPR spectroscopy and variable temperature magnetic susceptibility of the solution species indicate that there are two equivalent Mn(II) ions coupled by a ferromagnetic exchange interaction, having J ≥ 23 cm-1, fostered by two bridging semiquinones. This is evidenced by a paramagnetic ground state with a magnetic moment μeff = 6.78, electron spin resonance fine structure consistent with an apparent spin S = 3 and having zero-field splitting parameters of \D\ = 0.103 cm-1 and |E| = 0.011 cm-1, a nearly isotropic 11-line hyperfine structure for 55Mn with coupling constant \A\ = 45 ± 3 G, and a nearly isotropci g = 2. The quenching of the magnetic moment of the dimer with increasing temperature is interpreted to arise from the ferromagnetic coupling and, near room temperature, from an internal redox equilibrium in which Mn2(AQL)4L2 and possibly Mn2-(ASQ)2(AQL)2L2 (AQL = 2-acetyl-1,4-benzoquinol dianion) form. This complex is discussed in relation to its suitability as a model for the magnetic properties of the photosynthetic water-oxidizing enzyme.

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