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 bonding in transition metal inorganic and organometallic complexes
    sub title: new basis sets, linear semibridging carbonyls and thiocarbonyls, and oxidative addition of molecular hydrogen to square-planar iridium complexes
  name:
    name part: Sargent, Andrew Landman
    name part: 1963-
    role:
      role term: creator
  name:
    name part: Hall, Michael B.
    role:
      role term: degree supervisor.
  name:
    name part: Allen, Roland E.
    role:
      role term: degree committee member.
  name:
    name part: Cotton, F. Albert
    role:
      role term: degree committee member.
  name:
    name part: Lucchese, Robert R.
    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: 1991
    issuance: monographic
  language:
    language term: eng
  physical description:
    form: print
    extent: xiii, 157 leaves : illustrations ; 29 cm
  abstract: Approximate molecular orbital and ab initio quantum chemical techniques are used to investigate the electronic structure, bonding and reactivity of several transition metal inorganic and organometallic complexes. Modest-sized basis sets are developed for the second-row transition metal atoms and are designed for use in geometry optimizations of inorganic and organometallic complexes incorporating these atoms. The basis sets produce optimized equilibrium geometries which are slightly better than those produced with standard 3-21G basis sets, and which are significantly better than those produced with effective core potential basis sets. Linear semibridging carbonyl ligands in hetero bimetallic complexes which contain a coordinatively unsaturated late transition metal center are found to accept electron density from, rather than donate electron density to, these centers. Only when the secondary metal center is a coordinatively unsaturated early transition metal center does the semibridging ligand donate electron density to this center. Large holes in the d shell around the metal center are more prominent and prevalent in early than in late transition metal centers, and the importance of filling in these holes outweighs the importance of mitigating the charge imbalance due to the dative metal-metal interaction. Semibridging thiocarbonyl ligands are more effective donors of electron density than the carbonyl ligands since the occupied donor orbitals of π symmetry are higher in energy. The stereoselectivity of H2 addition to d^8 square-planar transition metal complexes is controlled by the interactions between the ligands in the plane of addition and the concentrations of electronic charge around the metal center as the complex evolves from a four-coordinate to a six-coordinate species. Electron-withdrawing ligands help stabilize the five-coordinate species while strong electron donor ligands contribute only to the destabilizing repulsive interactions. The relative therm…
  note: Typescript (photocopy).
  note: Vita.
  note: "Major subject: Chemistry."
  note: Ph. D. Texas A & M University 1991
  note: Includes bibliographical references.
  subject:
    topic: Transition metal complexes
    topic: Reactivity
  subject:
    topic: Metal-metal bonds
  subject:
    topic: Electronic structure
  subject:
    topic: Major chemistry
  identifier: http://gateway.proquest.com/openurl
  related item:
    location:
      url: http://gateway.proquest.com/openurl
  record info:
    record content source: TXA
    record creation date: 920228
    record change date: 20200904152603.0
    record identifier: in00001073256
    language of cataloging:
      language term: eng