Chemistry and Chemical Biology ETDs

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In chapter 1, the liquid/ liquid extraction of americium (III) from nitric and hydrochloric acid solutions with chloroform solutions of 2, 6 bis[ (diphenylphosphino) methyl] pyridine N, P. P' trioxide (ENOPOPO) is examined. Americium (III) is efficiently extracted from aqueous solutions at high nitric acid concentrations (Dam> 3000 at 6 M HNO3. The ligand dependency data suggest that two ligand molecules are coordinated to the americium. From hydrochloric acid solutions, ENPOPO exhibits modest extraction ability for americium (III) (Dam = 2.2 at5 M HCL) and can be efficiently back extracted from the organic phase at 0.1 M HCL. The ligand dependency data suggest that three ligand molecules are coordinated to the americium in the extraction complex. The coordination chemistry of ENPOPO with Pu (IV) and Eu (III) is also examined. In both cases, two molecules of ENPOPO are coordinated to the metal in a tridentate manner.

In chapter 2, the synthesis and characterization of organophosphorus ligands utilizing the Michael-type addition is explored. Diethyl vinylphosphonate and diphenylvinylphosphine oxide are allowed to react with various amines. The time of reaction is affected by the basicity of the amine, the steric bulk of the substituents on the amine, and the use of methanol as a solvent. Some of the phosphonate ligands undergo a degradation reaction in which a zwitterion is formed. These zwitterions are fully characterized, and in one case, X-ray crystallography is performed. The Michael-type addition was utilized to form new dendrimers that contain phosphoryl ligands. The ability of the model ligands and dendrimers to form coordination complexes is confirmed by infrared spectroscopy and X-ray crystallography.



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Department Name

Department of Chemistry and Chemical Biology

First Committee Member (Chair)

Robert T. Paine Jr.

Second Committee Member

William J. Kroenke

Third Committee Member

Cary Jacks Morrow