ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

Photochemically- and Thermally-Initiated Decomposition of Hexazadienes. An EPR and Cyclovoltammetric Study

K. Erentová, A. Staško, C. Scherer, B. Voit, and O. Nuyken

Department of Physical Chemistry, Faculty of Chemical Technology, Slovak Technical University, SK-812 31 Bratislava

Abstract: The investigated R¹-C₆H₄-N₂-NR²-NR²-N₂-C₆H₄-R¹ hexazadienes with R¹ = Cl, COCH³, COOCH₂CH₃ and R² = COCH₃ and CH₃ are characterized by cyclic voltammetry in acetonitrile solutions with an irreversible reduction wave in the potential range from -1.7 V to -2.0 V vs. saturated calomel electrode (SCE). After cathodic reduction they decompose under the formation of highly reactive radicals, which are terminated with solvent or support salt. Radicals R¹C₆H₄^., ^.CH₂CN, and ^.CHXCH₂CH₂CH₃ were found using spin trap technique. Upon irradiation under day-light and still more upon UV irradiation, hexazadienes decompose in CH₃CN solution in a few seconds and form primarily R¹C₆H₄^., ^.CH₂CN and finally   ^.CH₃ adducts to nitrosodurene (ND). Under thermally-initiated decomposition R¹C₆H₄^. and ^.H  adducts to ND were observed at 350 K.

Full paper in Portable Document Format: 502a60.pdf

Chemical Papers 50 (2) 60–64 (1996)