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mods:
  schema location: http://www.loc.gov/mods/v3 http://www.loc.gov/standards/mods/v3/mods-3-2.xsd
  title info:
    title: Oxidation of 2,6-di-t-butylphenol by molecular oxygen
    sub title: catalysis by cobaltous polyamine chelates
  name:
    name part: Bedell, Stephen Alan
    role:
      role term: creator
  name:
    name part: Hall, M. B.
    role:
      role term: degree committee member.
  name:
    name part: Martell, A. E.
    role:
      role term: degree supervisor.
  name:
    name part: O'Donovan, G. A.
    role:
      role term: degree committee member.
  name:
    name part: Zingaro, R. A.
    role:
      role term: degree committee member.
  name:
    name part: Texas A & M University
    role:
      role term: degree granting institution.
  type of resource: text
  genre: bibliography
  genre: Academic theses
  origin info:
    place:
      place term: xx
    date issued: 1983
    issuance: monographic
  language:
    language term: eng
  physical description:
    form: print
    extent: xi, 124 leaves : illustrations ; 29 cm
  abstract: The oxidation of 2,6-di-t-butylphenol by molecular oxygen in catalyzed by the (mu)-peroxo dicobalt(III) complexes formed by the ligands tetraethylenepentamine (tetren), 1,4,10,13-tetraaza-7-oxa-tridecane (taotd), 1,4,10,13-tetraaza-7-thiatridecane (tattd) and bis(pyridylmethyl)diethylenetriamine (pydien), as well as by the (mu)-peroxo, (mu)-hydroxo dicobalt(III) complexes formed by the ligands (bis)bipyridine (bipy), triethylenetetramine (trien), tris(aminoethyl)amine (tren), bis(pyridylmethyl)ethylenediamine (pyen), N,N'-bis(2-amino-ethyl)glycine (sdtma) and N,N'-ethylenediaminediacetic acid (sedda). This reaction is shown to be first order with respect to the concentration of both the cobalt-dioxygen complex and substrate. Reaction products are identified as the oxidative coupling product, 3,3',5,5'-tetra-t-butyldiphenoquinone and the partial oxygen insertion product, 2,6-di-t-butylbenzoquinone. Rate constants are given for the total reaction of the phenol as well as for the formation of the benzoquinone and diphenoquinone. Questions concerning the mechanism of reaction are raised, in conflict with previous workers' results which proposed the coordinated oxygen as the reactive intermediate. The oxidation of phenol in the presence of the dioxygen complexes investigated does not occur unless free molecular oxygen is present in solution. On the other hand, it was also found that insertion does not occur unless a dioxygen complex is present. Furthermore, the rate of the reaction varies greatly with the thermodynamic stability of the dioxygen complex. In addition to the oxidation catalysis studies, solution equilibria were investigated for the ligands taotd, tattd, and pyen in order to determine values for K(,O(,2)) and K(,O(,2))(''), the equilibrium constants for the addition of dioxygen to the preformed metal chelates to form the monobridged or dibridged oxygen complexes. To further understand the effects of the heteroatoms oxygen and sulfur in the formation of stabl…
  note: "Major subject: Chemistry."
  note: Typescript (photocopy).
  note: Vita.
  note: Ph. D. in Philosophy Texas A & M University 1983
  note: Includes bibliographical references (leaves 113-123).
  subject:
    topic: Catalysis
  subject:
    topic: Ligands
  subject:
    topic: Oxidation-reduction reaction
  subject:
    topic: Chemistry
  identifier: http://proxy.library.tamu.edu/login
  identifier: https://hdl.handle.net/1969.1/DISSERTATIONS-777527
  related item:
    location:
      url: http://proxy.library.tamu.edu/login
  related item:
    location:
      url: https://hdl.handle.net/1969.1/DISSERTATIONS-777527
  record info:
    record content source: TXA
    record creation date: 841128
    record change date: 20220104090509.0
    record identifier: in00000761119
    language of cataloging:
      language term: eng