74773-77-6Relevant academic research and scientific papers
Thermodynamic Destabilization of N-Centered Radical Cations by a γ-Keto Group
Nelsen, Stephen F.,Kessel, Carl R.,Grezzo, Loretta A.,Steffek, Daniel J.
, p. 5482 - 5485 (1980)
Vertical ionization potentials measured by PE spectroscopy and formal oxidation potentials measured by cyclic voltammetry are compared for several 9-substituted 9-azabicyclononan-3-one derivatives and their nonketo analogues.The compounds studied include hydrazines, 2-tetrazenes, p-phenylenediamines, p-tert-butylanilines, and tert-butylamines.The formal potential for one-electron oxidation is raised 3.2-7.4 kcal/mol by the presence of the keto group, depending on the amount of positive charge at N9 in the radical cation.In contrast, the formal potential for 3-oxobutyltrimethylhydrazine is only 0.5 kcal/mol higher than that of butyltrimethylhydrazine, although the change in vertical ionization potential is as large in the acyclic as in the bicyclic hydrazine.
