Degree Type

Dissertation

Date of Award

2006

Degree Name

Doctor of Philosophy

Department

Chemistry

First Advisor

Andreja Bakac

Second Advisor

James H. Espenson

Abstract

The superoxochromium ions LCr(H2O)OO2+ (L = (H2O)4 and [14]aneN4) and chromyl ion CrIVaqO2+ were shown to oxidize hydroperoxometal ions of Rh and Co to their corresponding superoxides. Kinetic isotope effects support hydrogen atom transfer from hydroperoxo- to superoxometal as the rate limiting step. Rate constants were determined and lie in the range of 17 to 130 M-1 s-1 for LCr(H2O)OO 2+ as oxidant and 103-104 M-1 s-1 for CrIVaqO2+ as oxidant. These rate constants are compared against other known hydrogen atom transfer reactions of hydroperoxo-, superoxo-, and oxometal ions.

DOI

https://doi.org/10.31274/rtd-180813-11343

Publisher

Digital Repository @ Iowa State University, http://lib.dr.iastate.edu/

Copyright Owner

Michael John Vasbinder

Language

en

Proquest ID

AAI3243550

File Format

application/pdf

File Size

97 pages

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