Experimental and theoretical study on the structure and reactions of 1-methoxypropane radical cations

Structure and mechanism of thermal and photochemical reactions of radical cations of methyl n-propyl ether (MPE) were studied in irradiated freonic matrices CFCl₃, CF₂ClCFCl₂, and CF₃CCl₃ at 77 K. The quantum chemical calculations of the structure of radical cations and products of their transformations were carried out with methods based on the density functional theory (DFT). Experimental and calculation results show that the MPE radical cations are characterized by substantial delocalization of spin density to the propyl group. The action of light on the MPE radical cations in a CF₃CCl₃ matrix at 77 K results in intramolecular rearrangement yielding the distonic radical cation ^.CH₂CH₂CH₂(OH⁺)CH₃. It was found that the primary MPE radical cations underwent irreversible transformation to CH₃CH₂CH₂OCH₂^. radical as a result of an ion-molecule reaction that occurred in a CF₂ClCFCl₂ matrix upon heating the sample to 110–120 K or in a CFCl₃ matrix upon increasing the solute concentration.Translated from Khimiya Vysokikh Energii, Vol. 39, No. 2, 2005, pp. 105–113.Original Russian Text Copyright © 2005 by Belevskii, Feldman, Tyurin.This revised version was published online in April 2005 with a corrected cover date.