Akademik Veri Yönetim Sistemi
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, cilt.87, sa.19, ss.3171-3178, 1991 (SCI-Expanded)
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.