Date of Graduation

Fall 12-13-2013

Document Type

Thesis

Degree Name

Master of Science (MS)

Department/Program

Chemistry

First Advisor

Jeff Curtis

Second Advisor

Kim Summerhays

Third Advisor

Larry Margerum

Abstract

The electron transfer (ET) self-exchange rates on a series of complexes of (NH3)5RuII/III L2+/3+ in D2O (where L is a substituted pyridyl ligand) were investigated by dynamic NMR measurements. Significant rate enhancement was observed for the cases of L = 3-phenylpyridine and 4-phenylpridine due to possible π-π stacking between Phpy ligands. These observations matche well with recent stopped-flow work by Mehmood on a similar set of related pseudo-self exchange reactions. Kinetics of the (NH3)5RuII/III (3-trifluoromethylpyridine)2+/3+ self-exchange reactions with addition of various simple/complex salts and hexacyano salts (K4M(CN)6 with M = Fe, Os and Ru) were also studied. The halide ions showed qualitatilvely-similar behavior compared to the stopped-flow work by Sista and the same quantitative decrease in the magnitude of salt effect as reported by Inagaki. The hexacyano salts were found to have a striking effect on the ET rate with a clear trend of Fe > >Os > Ru. This could be explained as a probable “superexchange” type mechanism dominated by the “hole-transfer” pathway based on the trend between the catalytic effect and the redox potential of the particular M(CN)4- ion. Kinetic modeling data also show the strongest catalytic effect of Fe which gives a ketx/ket of 126. Temperature-dependent experiments show that the rate enhancement of hexacyano series is due to a increased enthalpic barrier and less negative entropic barrier.

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