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: Electronic structure and reaction mechanism of transition metal complexes
    sub title: bond-stretch isomerism, methane activation on transient cyclopentadienylcarbonylrhodium, and ligand substitutions on metal nitrosyl carbonyl complexes
  name:
    name part: Song, Jun.
    role:
      role term: creator
  name:
    name part: Hall, Michael B.
    role:
      role term: degree supervisor.
  name:
    name part: Hedges, Richard M.
    role:
      role term: degree committee member.
  name:
    name part: Lucchese, Robert R.
    role:
      role term: degree committee member.
  name:
    name part: Williams, Glen N.
    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: 1992
    issuance: monographic
  language:
    language term: eng
  physical description:
    form: print
    extent: xii, 126 leaves : illustrations ; 29 cm
  abstract: Ab initio molecular orbital techniques are utilized to investigate the electronic structure and reaction mechanism of transition metal complexes. Our calculations at the levels of the restricted Hartree-Fock (RHF) and configuration interaction provide no evidence for the existence of bond-stretch isomers. For (LWOCl2) + (L=N,N'N''-trimethyl-1,4,7=triazacyclononane complexes, only the 2A' state can be identified as a ground state. The 2A'' is an excited state and the orbital crossing mechanism cannot explain the occurrence of two stable isomers. For cis-mer-MoOCl2(PR3)3 complexes, the second-order Jahn-Teller effect is too weak to cause the bond-stretch phenomenon. Methane oxidative-addition to a transient RhCp(CO) complex involves an agostic-like intermediate in the early stage of the reaction with a metal-CH dative interaction. The transition state shows C-H bond breaking and is stabilized by the Rh-C and Rh-H dative bonding interactions. The second-order Moller-Plesset perturbation calculations predict an exothermic reaction with a reaction energy of 30.6 kcal/mol, an intermediate with a stabilization energy of 14.8 kcal/mol and an activation barrier of 4.1 kcal/mol relative to the intermediate. CO substitution reactions on W(CO)4(NO)Cl and isoelectronic Re(CO)5Cl are examined through the construction of potential surfaces. The RHF calculations for the substitution by PMe3 on W(CO)4NOCl predict an associative mechanism with a 7-coordinate intermediate. The Laplacian of the total charge density displays a process in which electrons shift from the metal to the nitrogen, create an additional N lone pair and vacate a coordinate site for the entering ligand. Substitution by any PR3 on Re(CO)5Cl, however, proceeds by a dissociative or I[d] mechanism since the CO ligand cannot accommodate an additional electron pair. We also explored the influences of both the electron correlation and the basis set superposition error on the potential surfaces.
  note: Typescript (photocopy).
  note: Vita.
  note: "Major subject: Chemistry."
  note: Ph. D. Texas A & M University 1992
  note: Includes bibliographical references.
  subject:
    topic: Transition metal complexes
  subject:
    topic: Electronic structure
  subject:
    topic: Reactivity (Chemistry)
  subject:
    topic: Quantum chemistry
  subject:
    topic: Major 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: 931014
    record change date: 20200904152638.0
    record identifier: in00001160557
    language of cataloging:
      language term: eng