BONDING AND SPECTRA OF COORDINATION COMPOUNDS (thesis)
The electron spin-resonance spectra of chromium dibenzene cation and similar compounds are used to establish the nature of the chemical bond between the chromium and the carbon atoms. These are found to be essentially covalent'' compounds, the electrons being spread out over all the atoms of the complex. The optical spectra, both visible and ultraviolet, are presented and related to the bonding and electron-spin resonance spectra. The transitions from approximatehy 10,000 to 2000 A are assigned in terms of molecular orbitals. A comparative studv of copper acetate and of copper bisacetylacetonate is made on the basis of the optical and spin-resonance spcctra. The spectra are discussed in terms of a modifiedligand electrostatic field. The visible spectra are assigned to transitions between 3d levels of the copper ion, but ligand orbitals must be partly intermixed with these d orbitals in order to explain all the known data. This model is then extended to the more complicated case of vanadyl chelates. The optical spectra of seven vanadium (IV) complexes with BETA - diketones are discussed. Their relationship to the molecular structure of the chelates is established and correlated with properties of the metal ion and the ligand. Electron spin-resonance spectra of both solutions and single crystals of vanadium (IV) chelates are presented and related to the optical spectra. The methods of preparation of these compounds are described. The model developed from the discussion of vanadyl and copper chehates is extended to the chelates of all the metals of the first transition series. An explanation for the stabilities of complexes of these metals is offered in terms of this model. (auth)
- Research Organization:
- California. Univ., Berkeley. Radiation Lab.
- DOE Contract Number:
- W-7405-ENG-48
- NSA Number:
- NSA-12-006442
- OSTI ID:
- 4335772
- Report Number(s):
- UCRL-3867
- Country of Publication:
- United States
- Language:
- English
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