Sites of Reactivity During Ligand-Exchange Reactions in Octahedral Group VIB Metal Carbonyls Metadata

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Title

  • Main Title Sites of Reactivity During Ligand-Exchange Reactions in Octahedral Group VIB Metal Carbonyls

Creator

  • Author: Asali, Khalil Jamil
    Creator Type: Personal

Contributor

  • Chair: Dobson, Gerard R.
    Contributor Type: Personal
    Contributor Info: Major Professor
  • Committee Member: Desiderato, Robert
    Contributor Type: Personal
  • Committee Member: Russell, Benny
    Contributor Type: Personal
  • Committee Member: Theriot, L. J.
    Contributor Type: Personal

Publisher

  • Name: North Texas State University
    Place of Publication: Denton, Texas
    Additional Info: www.unt.edu

Date

  • Creation: 1979-12

Language

  • English

Description

  • Content Description: The site of initial metal-carbonyl bond-breaking during ligand-exchange reactions in a series of octahedral metal carbonyls of the type (L2)M(CO)4 (M = Cr, Mo, W; L2 = diphos, phen, dipy) has been determined employing infrared spectroscopy and Fourier transform nuclear magnetic resonance spectroscopy. The results of this study reveal, for all metal carbonyl complexes of the type mentioned above, that loss of CO occurs exclusively at an axial position (cis to the bidentate ligand, I^)• The dynamic nature of the five-coordinate intermediates, such as (diphos)Mo(CO)3, (phen)M(CO)3 (M = Cr, Mo, W), and (dipy)Cr(CO)3, which are generated in solution upon CO dissociation, is reported and discussed. The results of this investigation confirm that these intermediates are fluxional on the time scale of CO-exchange process. A mechanism which describes the site of initial metal-carbonyl bond-breaking and the fluxionality of the five-coordinate intermediate during ligand-exchange reactions in the complexes (L2)M(CO)4 is proposed. A kinetic study of reactions of W(CO)6 with pseudo-halide anions (NCS-, NCO-, CN-) has been initiated. The results indicate that these reactions proceed via a bimolecular path, which involves initial attack of the pseudo-halide anion at a carbonyl carbon of W(CO)6,
  • Physical Description: ix, 135 leaves : ill.

Subject

  • Keyword: liquid-exchange reactions
  • Keyword: metal-carbonyl bond-breaking
  • Keyword: octahedral metal carbonyls
  • Library of Congress Subject Headings: Chemical bonds.
  • Library of Congress Subject Headings: Exchange reactions.
  • Library of Congress Subject Headings: Metal carbonyls.
  • Library of Congress Subject Headings: Metal carbonyls -- Spectra.

Collection

  • Name: UNT Theses and Dissertations
    Code: UNTETD

Institution

  • Name: UNT Libraries
    Code: UNT

Rights

  • Rights Access: public
  • Rights Holder: Asali, Khalil Jamil
  • Rights License: copyright
  • Rights Statement: Copyright is held by the author, unless otherwise noted. All rights reserved.

Resource Type

  • Thesis or Dissertation

Format

  • Text

Identifier

  • Accession or Local Control No: 1002783479-Asali
  • Call Number: 379 N81d no.1480
  • UNT Catalog No.: b1189928
  • OCLC: 6419293
  • Archival Resource Key: ark:/67531/metadc330718

Degree

  • Academic Department: Department of Chemistry
  • Degree Discipline: Chemistry
  • Degree Level: Doctoral
  • Degree Name: Doctor of Philosophy
  • Degree Publication Type: disse
  • Degree Grantor: North Texas State University