The ESR. Spectrum of the Radical Anion of 1,1,2,2,9,9,10,10-Octafluoro [2.2]paracyclophane

✍ Scribed by Fabian Gerson; Hiroaki Ohya-Nishiguchi; Georges Plattner

• Publisher: John Wiley and Sons
• Year: 1982
• Tongue: German
• Weight: 278 KB
• Volume: 65
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.19820650213

✦ Synopsis

Abstract

The radical anion of 1,1,2.2,9,9,10, 10‐octafluoro[2.2]paracyclophane (1) has been generated by electrolytic reduction of 1 in 1,2‐dimethoxyethane (tetrabutylammonium perchlorate as the supporting salt). The hyperfine coupling constants of the eight ^19^F‐nuclei and the eight protons, a~f~ = 3.35 and a~H~ ≈ 0.10 mT, are qualitatively reproduced by INDO. calculations. According to these calculations, the singly occupied orbital of 1^⊖^ can be represented by an A~g~‐combination of two ‘symmetric’ benzene LUMO's, with a substantial transfer of spin population into the 2s‐AO's of the F‐atoms. Line‐width alternation in the ESR. spectrum of 1^⊖^ indicates an ion pairing of the radical anion with its counter‐ion Bu~4~N^⊖^. The energy barrier to the migration of the cation between two equivalent sites at the radical anion is determined as 14±2 kJ/mol.