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Stabilization and reactions of tetramethylurea radical cations in Freon matrices at 77 K: Intramolecular hydrogen transfer, ion-molecular reactions, and fragmentation by electron spin resonance study

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Abstract

ESR spectra for γ-irradiated at 77 K solutions /0.02–16%/ of tetramethylurea /TMU/ in CFCl3 and Freon-113 have been studied. TMU+. radical cations radiolytically produced in dilute solutions have been shown to undergo intramolecular hydrogen transfer upon photobleaching resulting in CH2N= type radical. Evidence for intermolecular proton transfer in TMU+. radical cations after annealing to phase transition temperature /110–120 K/ in Freon-113 was obtained. Primary radical cations of TMU+. at their ground state take part in ion-molecular reaction via proton transfer. Molecular cations in their excited states may undergo fragmentation producing Me2N radicals, which were trapped in liquid phase by t-BuNO as a spin trap.

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Belevsky, V.N., Belopushkin, S.I. Stabilization and reactions of tetramethylurea radical cations in Freon matrices at 77 K: Intramolecular hydrogen transfer, ion-molecular reactions, and fragmentation by electron spin resonance study. Journal of Radioanalytical and Nuclear Chemistry Letters 126, 53–67 (1988). https://doi.org/10.1007/BF02164803

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Keywords

  • Electron Spin Resonance
  • Proton Transfer
  • Radical Cation
  • Electron Spin
  • Phase Transition Temperature