Publication Date


Document Type


First Advisor

Mason, W. Roy||Brolles, Michael J.||Graham, Laurine L.

Degree Name

M.S. (Master of Science)

Legacy Department

Department of Chemistry




The complexes of some d? and d? platinum metal ions with the polyatomic ligands NH?, NO?? and SCN? were prepared for the purpose of obtaining additional and also more reliable electronic spectral data than those previously reported. The solutions for the present measurements were prepared in the dark and nonaqueous solvents were used except in the cases of the hexaammines and the hexanitro cobaltate (III) which were not soluble in the spectra-useful organic solvents. The drastic effect of the ordinary laboratory lighting on the spectra of these complexes is illustrated with the spectrum of hexathiocyanatorhodate (III) complex in methylene chloride solvent. In most cases higher values of ?[sub max] than those previously reported and in some complexes slight shifts in ?[sub max] are observed. The low temperature spectra of the hexathiocyanato and the hexanitro complexes of Rh(III) and Ir(III) were obtained using nonaqueous solvents that form rigid glasses at near 90°K. The aqueous solutions of magnesium chloride hexahydrate and of its mixture with aluminum chloride hexahydrate were also found to form rigid glasses at low temperatures. The room and low temperature spectrum of the hexaamminerhodate (III) perchlorate in the AlCl?/MgCl? mixture is reported. The magnetic circular dichroism (MCD) spectrum of Pt(NH?)?²? complex is reported and is shown to be consistent with its electronic absorption spectrum. The MCD terms observed for the other square planar complexes are also mentioned. The electronic spectral data obtained are compiled for g the d? systems with similar data for the Pt(IV) complexes and for d? complexes with the known data for the other Pd(ll), Au(III), and Pt(II) complexes. Band assignments based on the molecular orbital energy levels schemes for O[sub h], and D[sub 4h], symmetries are made. The T[sub h] symmetry is adopted for the discussion of the hexanitro complexes. In some cases alternate assignments to those already given are proposed.


Includes bibliographical references.||Includes illustrations.


viii, 70 pages




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