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: Reaction pathways in polynuclear metal carbonyls
  name:
    name part: Zalewski, David John.
    role:
      role term: creator
  name:
    name part: Anthony, R. G.
    role:
      role term: degree committee member.
  name:
    name part: Clearfield, Abraham
    role:
      role term: degree committee member.
  name:
    name part: Darensbourg, Donald J.
    role:
      role term: degree supervisor.
  name:
    name part: Darensbourg, Marcetta Y.
    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: 1986
    issuance: monographic
  language:
    language term: eng
  physical description:
    form: print
    extent: xvii, 208 leaves : illustrations ; 29 cm
  abstract: This study concentrates on the reactivity, characterization, and synthesis of transition metal clusters. The primary goals behind this investigation were: (1) to determine whether or not electronic information can be transmitted along the metal-metal bonds of a cluster; (2) to access the importance of metal-metal bond homolysis during substitution reactions; (3) to identify the reactive sites of a cluster; and (4) to develop a systematic route to the synthesis of new transition metal cluster compounds. A kinetic investigation of the ligand substitution processes of Co₄(CO)₉(tripod) {tripod = HC(PPh₂)₃} and its phosphine substituted derivatives is reported. In this cluster system, the tripod group coordinates to three different metal atoms, reducing the chance of cluster fragmentation. Rate constants and activation parameters for the CO displacement reactions of the cobalt-tripod clusters were found to be consistent with a dissociative process. The electronic and steric influences of the coordinated phosphine ligands are examined. In order to accurately access the kinetic information and determine exactly how the phosphine ligands affect the reaction rate, the molecular arrangement of these clusters must be firmly established. In this regard we report the X-ray structures of several key species: Co₄(CO)₉(tripod); Co₄(CO)₈(PMe₃)₂(tripod); Co₄(CO)₇(PMe₃)(,2)(tripod); and Co₄(CO)₇(dppm)(tripod) {dppm = H₂C(PPh₂)₂}. The ligand framework in the double-chelated cluster, Co₄(CO)₇(dppm)(tripod) hinders the intramolecular ligand migration process. Therefore, this cluster can be used to determine the exact site a carbon monoxide group dissociates from. Trinuclear {[M₃(CO)₁₂S][PPN₂)} and tetranuclear {[M₄(CO)₁₇S][PPN₂)} group six (M = Cr,Mo,W) clusters have been synthesized by utilizing a sulfur atom as a template to collect mononuclear metal fragments. This method allows the stepwise construction both homonuclear and heteronuclear clusters. Both the intramolecular and intermol…
  note: Typescript (photocopy).
  note: Vita.
  note: Ph. D. in Chemistry Texas A & M University 1986
  note: Includes bibliographical references (leaves 200-207).
  subject:
    topic: Metal-metal bonds
  subject:
    topic: Organometallic chemistry
  subject:
    topic: Transition metal compounds
    topic: Synthesis
  subject:
    topic: Major chemistry
  identifier: http://proxy.library.tamu.edu/login
  identifier: https://hdl.handle.net/1969.1/DISSERTATIONS-18468
  related item:
    location:
      url: http://proxy.library.tamu.edu/login
  related item:
    location:
      url: https://hdl.handle.net/1969.1/DISSERTATIONS-18468
  record info:
    record content source: TXA
    record creation date: 880329
    record change date: 20220104090740.0
    record identifier: in00000012107
    language of cataloging:
      language term: eng