THE ELECTRONIC STRUCTURE OF ORGANOMETALLIC CARBONYL, NITROSYL, THIONITROSYL, AND CYANIDE COMPLEXES BY GAS PHASE X-RAY AND ULTRAVIOLET PHOTOELECTRON SPECTROSCOPY.

Persistent Link:
http://hdl.handle.net/10150/184525
Title:
THE ELECTRONIC STRUCTURE OF ORGANOMETALLIC CARBONYL, NITROSYL, THIONITROSYL, AND CYANIDE COMPLEXES BY GAS PHASE X-RAY AND ULTRAVIOLET PHOTOELECTRON SPECTROSCOPY.
Author:
HUBBARD, JOHN LEE.
Issue Date:
1982
Publisher:
The University of Arizona.
Rights:
Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
Abstract:
Transition metal-ligand interactions in several groups of closely related organometallic complexes are discussed from the results of both valence and core photoelectron experiments. Particular attention is given to the novel experimental aspects, including a charged particle oscillator He II source, sample introduction and containment, and data collection and spectral analysis procedures not normally associated with gas phase photo-electron spectroscopy. The application of the ionization experiments begins with a reassessment of the bonding in the group VIb metal hexacarbonyls. He I ionization data of unprecedented quality for the predominantly metal d t₂g level of Cr(CO)₆ and W(CO)₆ reveals for the first time the presence of metal-carbon vibrational fine structure. These positive ion M-C stretching frequencies are significantly reduced from neutral ground state values, giving direct evidence of the pi back-bonding nature of the t₂g level. The next chapter focuses on the comparison of the metal-nitrosyl interactions in the trans-X-W(CO)₄NO complexes to the isoelectronic/isostructural metal-carbonyl interactions in the X-Re(CO)₅ complexes (X = Cl,Br,I). A further comparison of carbonyl and nitrosyl bonding, as well as the first photoelectron assessment of metal-thionitrosyl bonding, is addressed in the next chapter by comparing the valence and core ionization data for CpCr(CO)₂NO and CpCr(CO)₂NS (Sp = η⁵-C₅H₅) to the data reported earlier for CpMn(CO)₃ and CpMn(CO)₂CS. The final chapter of the dissertation compares the electronic structure of the CpFe(CO)₂X complexes to their CpCr(NO)₂X analogs (X = Cl,Br,I,CH₃,CN). The essence of this work fully contrasts the Fe(CO)₂ and Cr(NO)₂ functional groups.
Type:
text; Dissertation-Reproduction (electronic)
Keywords:
Transition metals.; Ligand field theory.; Photoelectron spectroscopy.; Ultraviolet spectroscopy.; X-ray spectroscopy.; Organometallic compounds.
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Chemistry; Graduate College
Degree Grantor:
University of Arizona
Advisor:
Lichtenberger, Dennis

Full metadata record

DC FieldValue Language
dc.language.isoenen_US
dc.titleTHE ELECTRONIC STRUCTURE OF ORGANOMETALLIC CARBONYL, NITROSYL, THIONITROSYL, AND CYANIDE COMPLEXES BY GAS PHASE X-RAY AND ULTRAVIOLET PHOTOELECTRON SPECTROSCOPY.en_US
dc.creatorHUBBARD, JOHN LEE.en_US
dc.contributor.authorHUBBARD, JOHN LEE.en_US
dc.date.issued1982en_US
dc.publisherThe University of Arizona.en_US
dc.rightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.en_US
dc.description.abstractTransition metal-ligand interactions in several groups of closely related organometallic complexes are discussed from the results of both valence and core photoelectron experiments. Particular attention is given to the novel experimental aspects, including a charged particle oscillator He II source, sample introduction and containment, and data collection and spectral analysis procedures not normally associated with gas phase photo-electron spectroscopy. The application of the ionization experiments begins with a reassessment of the bonding in the group VIb metal hexacarbonyls. He I ionization data of unprecedented quality for the predominantly metal d t₂g level of Cr(CO)₆ and W(CO)₆ reveals for the first time the presence of metal-carbon vibrational fine structure. These positive ion M-C stretching frequencies are significantly reduced from neutral ground state values, giving direct evidence of the pi back-bonding nature of the t₂g level. The next chapter focuses on the comparison of the metal-nitrosyl interactions in the trans-X-W(CO)₄NO complexes to the isoelectronic/isostructural metal-carbonyl interactions in the X-Re(CO)₅ complexes (X = Cl,Br,I). A further comparison of carbonyl and nitrosyl bonding, as well as the first photoelectron assessment of metal-thionitrosyl bonding, is addressed in the next chapter by comparing the valence and core ionization data for CpCr(CO)₂NO and CpCr(CO)₂NS (Sp = η⁵-C₅H₅) to the data reported earlier for CpMn(CO)₃ and CpMn(CO)₂CS. The final chapter of the dissertation compares the electronic structure of the CpFe(CO)₂X complexes to their CpCr(NO)₂X analogs (X = Cl,Br,I,CH₃,CN). The essence of this work fully contrasts the Fe(CO)₂ and Cr(NO)₂ functional groups.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.subjectTransition metals.en_US
dc.subjectLigand field theory.en_US
dc.subjectPhotoelectron spectroscopy.en_US
dc.subjectUltraviolet spectroscopy.en_US
dc.subjectX-ray spectroscopy.en_US
dc.subjectOrganometallic compounds.en_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorLichtenberger, Dennisen_US
dc.identifier.proquest8227356en_US
dc.identifier.oclc682948611en_US
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