title: Theoretical Evidence for the Relevance of n(F) → σ*(C-X) (X = H, C, O, S) Stereoelectronic Interactions.
abstract: Theoretical calculations on r-1,c-3,c-5-trifluorocyclohexane (1), r-2,c-4,c-6-trifluoro-1,3,5-trioxane (2), and r-2,c-4,c-6-trifluoro-1,3,5-trithiane (3) confirm the importance of n(F) → σ*(C-Y)gem, where Y = H, C, O, S, hyperconjugative interactions; that is, contrary to common wisdom, fluorine is a good lone pair electron donor toward geminal sigma bonds. This conclusion is in line with the recent observations reported by O'Hagan and co-workers, who synthesized and examined all-cis 1,2,3,4,5,6-hexafluoro-cyclohexane (Nat. Chem. 2015, 7, 483-488).
authors.affiliation: Departamento de Química, Centro de Investigación y de Estudios Avanzados, Instituto Politécnico Nacional , Apartado Postal 14-740, 07000 México, D. F. Mexico.
authors.forename: Eusebio
authors.initials: E
authors.lastname: Juaristi
authors.affiliation: Instituto de Química Física Rocasolano, CSIC , Serrano 119, 28006 Madrid, Spain.
authors.forename: Rafael
authors.initials: R
authors.lastname: Notario