rdf-syntax-grammar
mods:
  schema location: http://www.loc.gov/mods/v3 http://www.loc.gov/standards/mods/v3/mods-3-2.xsd
  title info:
    title: Chemical and physical studies of paramagnetic transition metal carbonyls
  name:
    name part: Springs, Jerry J.
    name part: 1962-
    role:
      role term: creator
  name:
    name part: Darensbourg, Marcetta Y.
    role:
      role term: degree supervisor.
  name:
    name part: Anthony, Rayford G.
    role:
      role term: degree committee member.
  name:
    name part: Hall, Michael B.
    role:
      role term: degree committee member.
  name:
    name part: Krusic, Paul J.
    role:
      role term: degree committee member.
  name:
    name part: Rosynek, Michael P.
    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: 1989
    issuance: monographic
  language:
    language term: eng
  physical description:
    form: print
    extent: xiii, 166 leaves : illustrations ; 29 cm
  abstract: The group 6 anionic transition metal alkyls, CH₃W(CO) ₅- (M = Cr, W) were found to react with organic substrates via radical pathways. No reactivity involving CH₃ - group transfer was observed. With organometallic substrates, the group 6 anionic alkyls reacted to give products indicative of radical intermediates. For example, the neutral metal alkyl CH₃Mn(C0)₅ reacted with anionic alkyls to give the heterobimetallic species MnM(CO)₁₀- and acetone as major products. Electron transfer from CH₃W(CO)₅- to C0₂(CO)₈ resulted in dimer reduction and disruption yielding CoW(CO)₉- and acetone. The production of acetone is proposed to occur via an oxidatively promoted migratory insertion pathway involving 17-electron intermediates. The anionic group 6 acyl [Li] [CH₃ C(0)W(CO)₅] underwent a photo-induced electron transfer to give a neutral acyl radical characterized by ESR spectroscopy. The ESR spectrum of a solution of [Li] [CH₃C(0)W(CO)₅] flowed together with [Fc] [BF₄] indicated a septet with ¹⁸³W coupling. The thermally unstable radical was tentatively assigned to the diacyl (OC)₄ W(C(0)CH₃)₂ the dimeric diacetyl bridged (OC)₅W(0)C(CH₃ )-C(CH)₃(0)W(CO)₅, or the oxygen-bound chelate (OC)₄W(OC(CH₃)C(CH₃)0⁻) . The radical species was transient and only observed under flow conditions. The oxidation of the chromium thiolate complexes, RSCr(CO)₅- (R = Et, t-Bu) resulted in the sulfur-coupled dimers (μ-RSSR)Cr₂(CO)₁₀ via dimerization of the 17-electron species [RSCr(CO)₅]. Attempts to characterize the short-lived monomer radicals using ESR were unsuccessful. A series of bridging chromium thiolates, μ-RSCr₂ (CO)₁₀- (R = H, Me, Et, i-Pr, t-Bu, Ph) were oxidized and the resulting radicals were characterized by ESR and IR v(C0) at low temperatures. The radicals were assigned to the neutral species [μ-RSCr₂(CO)₁₀]. Protonation at the sulfur site in RSCr(CO)₅- leads to a new series of thiol chromium complexes, (RSH)Cr(CO)₅ (R = Et, i-Pr, t-Bu). Alternatively, reaction of Cr(C0)₅. THF wi…
  note: by Jerry J. Springs.
  note: Typescript (photocopy).
  note: Vita.
  note: "Major subject: Chemistry."
  note: Ph. D. Texas A & M University 1989
  note: Includes bibliographical references.
  subject:
    topic: Organometallic compounds
  subject:
    topic: Transition metal compounds
  subject:
    topic: Electron paramagnetic resonance
  subject:
    topic: Infrared spectroscopy
  subject:
    topic: Electron paramagnetic resonance
  subject:
    topic: Infrared spectroscopy
  subject:
    topic: Organometallic compounds
  subject:
    topic: Transition metal compounds
  subject:
    topic: Chemistry
  identifier: http://proxy.library.tamu.edu/login
  related item:
    location:
      url: http://proxy.library.tamu.edu/login
  record info:
    record content source: TXA
    record creation date: 901115
    record change date: 20200904152456.0
    record identifier: in00000930222
    language of cataloging:
      language term: eng