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Date of Award

1973

Document Type

Dissertation

Degree Name

Doctor of Philosophy (Ph.D.)

Department

Graduate School

First Advisor

Herschel Frye

First Committee Member

Francis W. Sayre

Second Committee Member

J. F. Rodriguez

Third Committee Member

Charles A. Matuszak

Fourth Committee Member

Richard P. Dodge

Abstract

The purpose of this study was to prenare and characterize the palladium (II) and platinum (II) chelates of 1-pyrrolidineacetic acid, 1-piperidineacetic acid, and hexahydro-1-azepineacetic acid.

The ligands were prepared by reacting the cyclic secondary arnines (pyrrolidine, piperidine, and hexahydroazepine) with sodium chloroacetate. The resulting cyclic tertiary amino acids were saponified and, finally, converted to the hydrochloride salts by neutralization with hydrochloric acid.

The chelates were prepared by adding 1.0 millimole of K2PdC14 or K2PtC14 to a solution made by dissolving 2.0 Millimoles of amino acid hydrochloride in 25 ml. of water. The pH was adjusted to 7.4 and the solution was steam heated for an hour. That volume was reduced to 25 ml. by evaporation. Crystals began to form in one to three days and crystallization was complete in seven days. The products were not recrystallized since no appropriate solvents could be found. The six coordination compounds prepared are unreported in the literature.

Elemental analyses, UV-visible spectra, and IR spectra were utilized to elucidate the structure of the coordination compounds. 'l'he amino acids form chelates between the carboxyl and amine groups with the form: M(amino acid)2 . The three amino acids are believed to form square planar complexes with palladium and platinum. It is proposed that the six new compounds are:

  • cis bis 1-pyrrolidineacetato palladium (II),
  • cis bis 1-pyrrolidineacetato platinum (II),
  • cis bis 1-piperidineacetato palladium (II) ,
  • cis bis 1-pioeridineacetato platinum (II),
  • trans bis hexahydro-1-azepineacetato palladium (II) ,
  • trans bis hexahydro-1-azepineacetato platinum (II).

The ionization constants of the three amino acids were determined using the poteniometric method of Albert and Sergeant. The ionization constants of 1-pyrrolidineacetic acid and hexahydro-1-azepineacetic acid are unreported in the literature.

The stability constants of all six of the coordination compounds were determined using the method of Albert and Serqeant. This method involved the potentimletric titration of a solution 0.005 molar in K2PdCl4 or K2PtCl4 and 0.01 molar in amino acid hydrochloride with o.1N ootassium hydroxide at 25°C. The stability constants of the chelates differ only slightly with the ring structure of the amino acids under investigation. The stability constants of the palladium chelates are about 102 greater than the corresponding platinum chelates

Pages

71

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Chemistry Commons

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