Includes bibliographical references. / Metal-nitrogen stretching vibrations in Co(II), Ni(II), Cu(II) and Zn(II) chloride 4-methylaniline complexes are assigned by ¹⁵N-labelling in conjunction with a consideration of the relative crystal field stabilizition energies of the metal ions. Bands in the ultraviolet electronic spectra of Cu(II) β-ketoenolate complexes are more conclusively assigned by comparison of the spectra of the β-ketoenolates, their sodium salts and the copper complexes. The effect of ligand substitution on the infrared spectra of Cu(II) benzoylacetanilide complexes and their methanol adducts is used to assign copper-oxygen stretching frequencies. The effect of ligand substitution on the ultraviolet electronic spectra is used to estimate the extent of π-interaction in these complexes. The infrared spectra of six ¹⁵N-labelled Co(II), Ni(II), Cu(II) and Zn(II) N-salicylideneanthranilate complexes yield assignments of metal-ligand and certain ligand vibrations. These assignments are supported by observing the effects of metal ion and ligand substitution on the spectra. The shifts observed in the metal-ligand stretching frequencies are related to the relative crystal field stabilization energies of the metal ions and to the electron releasing and withdrawing capacities of the ligand substituents. Assignments of metal-ligand vibrations in the infrared spectra of Ni(II) and Cu(II) benzoylbenzilidenehydrazone complexes and Co(II), Ni(II), Cu(II) and Zn(II) benzoylsalicylidenehydrazone complexes are made by observing the effects of metal ion and ligand substitution on the spectra. The infrared spectra of three ¹⁵N-labelled Ni(II), Co(II) and Cu(II) triarylformazan complexes yield assignments of metal-ligand and certain ligand vibrations. The effect of ligand substitution on the infrared spectra of Ni(II) triarylformazan complexes is related to the electron releasing or withdrawing capacities of the substituents. A total of 168 complexes, of which 131 have not previously been reported, has been synthesized and discussed.
| Identifer | oai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:uct/oai:localhost:11427/12470 |
| Date | January 1975 |
| Creators | Johnson, Peter Robin |
| Contributors | Thornton, David A |
| Publisher | University of Cape Town, Faculty of Science, Department of Chemistry |
| Source Sets | South African National ETD Portal |
| Language | English |
| Detected Language | English |
| Type | Doctoral Thesis, Doctoral, PhD |
| Format | application/pdf |
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