Date of Award
Doctor of Philosophy
James H. Espenson
The superoxochromium ions LCr(H2O)OO2+ (L = (H2O)4 and 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.
Digital Repository @ Iowa State University, http://lib.dr.iastate.edu/
Michael John Vasbinder
Vasbinder, Michael John, "Oxidations of organic and inorganic substrates by superoxo-, hydroperoxo-, and oxo-compounds of the transition metals " (2006). Retrospective Theses and Dissertations. 3068.