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    Characterization and Thermodynamic Analysis of a Series of MnIII-OH Complexes that undergo Hydrogen Atom Transfer Reactions

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    Available after: 2020-12-31 - Kinetics_TEMPOH_negative10C_2per and 10 perc water (34.01Kb)
    Issue Date
    2018-12-31
    Author
    Munasinghe, Aruna Indeewara
    Publisher
    University of Kansas
    Format
    77 pages
    Type
    Thesis
    Degree Level
    M.S.
    Discipline
    Chemistry
    Rights
    Copyright held by the author.
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    Abstract
    Abstract Mononuclear MnIII-hydroxo motifs employ hydrogen atom transfer (HAT) reactions in biology and synthetic systems to oxidize a wide range of CH or OH bonds. Extensive studies on high valent Fe and Mn model systems exist, while studies on low and mid valent manganese complexes are less explored. In an effort to broaden the knowledge on structure and reactivity relationships of MnIII-OH motifs in HAT reactivity, a novel MnIII-OH complex is introduced to the [MnIII(OH)(dpaqR)](OTf) series. Understanding the HAT reactivity of MnIIIOH moieties in biological reactions rely on their reaction driving forces that are governed by the redox potential of the oxidant and the pKa value of the proton abstractor. However determining these thermodynamic parameters for biological systems is difficult. Alternatively, an understanding about these parameters can be obtained by studying their corresponding synthetic model systems. In an effort to understand the HAT step of the Mn-lipoxygenase catalytic cycle, a series of [MnII(OH2)(dpaqR)]+ complexes were prepared.
    URI
    http://hdl.handle.net/1808/29563
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    KU Libraries
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    Contact KU ScholarWorks
    785-864-8983
    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    785-864-8983

    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    Image Credits
     

     

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