Date of Award

6-1976

Document Type

Open Access

Degree Name

Masters of Science

Department

Chemistry

First Advisor

Charles F. Weick

Language

English

Abstract

Previous studies indicate substitution of bromide ion for chloride ion in [Au(Et4dien~H)c.i] +occurs at a rate almost independent of the bromide ion concentration, while similar reactions with [Au(dien-H)Cl]+, [Au(Me2dien-H)c!]+ and [Au(Me4dien-H)c~+ show rates dependent on bromide ion concentration as usually encountered for square planar complexes. There is retardation of the reaction by steric and electronic effects with increased N-alkyl substitution of the triamine. It has also been postulated that substitution of [Au(Et2dien-H)cJ]+ proceeds via a ring-opening mechanism. The purpose of this research was to study further the effect of steric hindrance on rates of substitution of two additional gold(III) complexes. The complexes of Me5dien and MeEt4dien with gold(III) were prepared and investigated, As observed with other less methyl substituted gold(III) dien complexes the substitution reaction of [Au(Me5dien)C:£j 2+ with bromide ion is dependent on the bromide ion concentration. The results of the reaction rate studies on [Au(MeEt4dien)CY Z+ with bromide ion can most easily be rationalized in terms of the previously postulated ring-opening mechanism.

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