Thesis--Chemistry : Columbia : 1940.

Thesis (Ph. D.)--University of Washington, 2004. / Vita. Includes bibliographical references (leaves 58-71).

Thesis (Ph. D.)--Columbia University, 1938. / Vita.

Diss. - Columbia University.

Thesis--Columbia University. / Vita. Bibliography: p. 65-66.

Thesis (Ph. D.)--Columbia University, 1942. / Vita. Bibliography: p. 14.

Thesis (Ph. D.)--Columbia University, 1941. / Vita. Bibliography: p. 20.

There is not, at this time, a simple method for the simultaneous determination of As (III) and As (V) at trace levels. The development of such as method is needed, as the toxicities of these two species differ so greatly. As (III) and As (V) are polarographically reducible in the presence of excess catechol, but the wave produced by As (V) is depended on time, pH and catechol concentration as well as As (V) concentration. In order to understand this behavior, determination of formation constants for any complex species present were needed to identify which species is electroactive. The literature to date on the subject of As (V) – catechol compounds has shown that there is not a thorough understanding of what species are present and what their stabilities are.

The dissertation describes research work on development of bimetallic heterogeneous catalysts for oxidation of organic compounds. Binuclear metal complexes are an interesting class of compounds due to their catalytic activity. The approach involves anchoring a triketone ligand to Cab-O-Sil via a linker. Specifically, silica gel was allowed to react with p-chloromethylphenyltrimethoxysilane followed by coupling with deprotonated triketone compounds. The viability of this approach was verified by performing the benzylation reaction of triketones with benzyl halides under basic conditions. The benzylation of 2,4,6-heptanetrione and 1,5-diphenyl-1,3,5-pentanetrione is achieved with benzyl bromide using n-tetrabutylammonium fluoride as base. These benzylation reaction conditions were used to attach the triketones to the surface-attached linker. Once the ligand is attached to the silica gel, the catalyst is formed by coordinating two copper(II) ions from solution to the deprotonated triketone. The coordination of copper(II) ions to the triketone was monitored using UV-vis spectroscopy. The modified silica gel is characterized by diffuse reflectance infrared Fourier spectroscopy (DRIFTS), and thermal gravimetric analysis (TGA) at the different stages of catalyst formation. All techniques indicated significant attachment of linker and triketone to the support. The oxidation of 3,5-di-tert-butyl catechol (DTBC) and benzyl alcohol was carried out under aerobic conditions using these catalysts. The kinetics of the DTBC oxidation and benzyl alcohol oxidation was studied using bimetallic and monometallic catalytic systems. The copper complexes of the triketone ligands were also evaluated as catalysts for the oxidation of DTBC. New bimetallic metal complexes with triketone ligands having a benzyl group were synthesized and characterized by high resolution mass spectroscopy and IR spectroscopy. In addition to a detailed description of the synthesis and characterization of new triketone compounds, and the heterogeneous catalyst systems, a comparison of the kinetics of the oxidation of DTBC using these catalysts will be discussed.

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