Author

Beyene

Date of Award

12-1987

Degree Name

Master of Arts

Department

Chemistry

First Advisor

Dr. Ralph K. Steinhaus

Second Advisor

Dr. Dean W. Cooke

Third Advisor

Dr. James A. Howell

Access Setting

Masters Thesis-Open Access

Abstract

The reaction between N-(2-pyridylmethyl)iminodiacetatonickel(II) and copper(II) was studied spectrophotometrically between pH 2.30 and 3.30 over a 10-fold variation in copper concentration at an ionic strength of 1.25M, and a temperature of 25.0+0.1oC. The reaction is first order in both NiPyIDA and copper(II). Terms involving proton attack and a copper dependent dissociation of the nickel complex were resolved from the data. Evidence is given for a stepwise unwrapping mechanism PyIDA from the nickel complex, followed by copper attack to give a dinuclear intermediate. A general mechanism is presented which is consistent with the kinetic data.

Comparisons to analogous nickel-aliphatic exchange reactions with copper(II) are made and used to account for the important kinetic features of the reaction which involve the absence of an order shift in the copper concentration as the copper concentration is increased.

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