ELECTRON-PARAMAGNETIC RESONANCE AND THEORETICAL-STUDY OF DIBENZYLMERCURY AND DIPHENYLMERCURY RADICAL CATIONS


RHODES C., GLIDEWELL C., AGIRBAS H.

JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, vol.87, no.19, pp.3171-3178, 1991 (Journal Indexed in SCI) identifier identifier

  • Publication Type: Article / Article
  • Volume: 87 Issue: 19
  • Publication Date: 1991
  • Doi Number: 10.1039/ft9918703171
  • Title of Journal : JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS
  • Page Numbers: pp.3171-3178

Abstract

Radical cations of dibenzylmercury and its p-X derivatives (X = Me, MeS, MeO, Cl) and of diphenylmercury and its p-X derivatives (X = Cl, Et, Me, MeO) have been generated by gamma-radiolysis of dilute solutions of the parent compounds in CFCl3 matrices at 77 K. The EPR results for the dibenzylmercury series show all members to be sigma-u-radical cations with singly occupied molecular orbitals approximating to the form (I). The parallel and perpendicular \ + 1/2 > components of the Hg-199 spectrum are almost coincident, giving an intense low-field isotropic line: this shows a substructure typical of an anisotropic doublet coupling, and arises from a single solvent fluorine atom, but is unprecedentedly large for radical-cation superhyperfine couplings in freon matrices. These additional couplings were absent when the experiments were repeated using a CCl4 matrix which confirms the F-19 assignment.