Alternate Author Name(s)

Dr. Warren Miller, PhD '70

Document Type

Dissertation

Date of Award

1970

Keywords

Coordination, compounds, Rare earths, Chemical kinetics

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Advisor

Stanley K. Madan

Series

Science and Mathematics

Abstract

Coordination chemistry can be divided into two very general areas, one being the study of very reactive, labile, systems, and the other being the investigation of relatively inert species. With the hope of learning something about both of these areas, and with a desire to make a contribution to each, this thesis is comprised of two separate parts, the first dealing with the very labile complexes of the Ianthanide elements, and the second dealing with the relatively inert complexes of Co(III).

In Section A of Part I, a summary of past work in the area of lanthanide complexes with oxygen donor ligands is presented. In Section B, the synthesis and characterization of several lanthanide perchlorate complexes of y-butyrolactam, and N-methyl-y-butyrolactam are reported. A similar study of the lanthanide nitrate complexes of Y-butyrolactam is reported in Section C. In Section D of Part I, a study of the fluorescence behavior of the europium and terbium perchlorate complexes of 2,2‘-bipyridine 1,1'-dioxide is described. The final section of Part I describes the direction in which the work described in this thesis can be extended.

In Section A of Part II, the present state of knowledge on the acid hydrolysis reactions of Cr(III) and Co(III) halo-amine complexes is reviewed. In Section B a kinetic study of the acid hydrolysis of bromoaquo (triaminotriethylamine) cobalt(III) ion is reported and the data compared with that of other Cr(III) and Co(III) systems. A similar study for the corresponding chloroaquo complex is reported in Section C. In the last section of Part II, possible future research problems arising from the author's work are discussed.

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