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Access Type

WSU Access

Date of Award

January 2017

Degree Type

Thesis

Degree Name

M.S.

Department

Chemistry

First Advisor

Charles H. Winter

Abstract

Treatment of tetrakis(dimethylamido)zirconium with four equivalents of primary and secondary amides in refluxing toluene, followed by sublimation of the crude products afforded tetrakis(N-tert-butylacetamido)zirconium, tetrakis(N-isopropylisobutyramido)zirconium, tetrakis(N-isopropylacetamido)-zirconium, tetrakis(N-methylacetamido)zirconium, and tetrakis(N-tert-butylformamido)zirconium as colorless crystalline solids. The structural assignments for the new complexes were based upon spectral and analytical data and by X-ray crystal structure determinations for tetrakis(N-tert-butylacetamido)zirconium, tetrakis(N-isopropylacetamido)zirconium, tetrakis(N-methylacetamido)zirconium, and tetrakis(N-tert-butylformamido)zirconium. These complexes are monomeric in the solid state, with eight-coordinate metal centers surrounded by four k2-amidate ligands. Solid state decomposition temperatures for the zirconium complexes range between 218-335 degrees Celsius.

Treatment of tris(tert-butylperoxy)borane with one equivalent of 4-dimethylaminopyridine or ammonia, quantitatively yielded colorless crystalline complexes. The structural assignment for the 4-dimethylaminopyridine adduct was based upon spectral and X-ray crystal structure determinations.

The thermal stability and volatility evaluation of bis[tris(pyrazolyl)borate]ruthenium(II) is reported as a potential precursor for the deposition of ruthenium containing films.

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