Carbon-hydrogen bond activation in benzosemiquinones via radical-radical coupling with nitric oxide

ORGN 149

Steven J. Peters, sjpeter@ilstu.edu, Trisha M. Blood, tmblood@ilstu.edu, and Amy M. Sudhoff, sjpeter@ilstu.edu. Department of Chemistry, Illinois State University, MS 4160, Normal, IL 61790
Nitric oxide (NO) is important in many chemical processes that occur in mammalian systems. Quinones and semiquinones play a role in biological redox and electron-transfer processes. A unique reaction between these two compounds has been observed. The potassium metal reduction of p-benzoquinone(C6H4O2) in hexamethylphoshoramide (HMPA) followed by exposure to NO gas results in the coupling between NO and p-benzosemiquinone. Re-exposure to more metal generates two new species which are observed via EPR spectroscopy; both are substituted p-benzosemiquinone systems with a nitrogen functional group. Use of 15NO reveals that the nitrogen in these products does not come from the 15NO, but from a condensation reaction with the HMPA. The initial coupling of 15NO and C6H4O2.- results in a concerted C-H bond activation and attack of the HMPA solvent. Nitroxyl (H15NO) is also produced, and 15N-NMR analysis reveals the presence of 15N-nitrous oxide(15N15NO) formed from the dimerization of H15NO.