Density Functional Study of Interactions between Fluorinated Cyclohexanes and Arenes

Author(s)

Cormanich, Rodrigo A. ^{[1, 2, 3]} ; Durie, Alastair ^{[2, 3]} ; Bjornsson, Ragnar ^[4] ; Rittner, Roberto ^[1] ; O'Hagan, David ^{[2, 3]} ; Buehl, Michael ^{[2, 3]}

Affiliation

^[1] Univ Estadual Campinas, Inst Chem, BR-13083970 Campinas, SP - Brazil

^[2] Univ St Andrews, EastChem Sch Chem, St Andrews KY16 9ST, Fife - Scotland

^[3] Univ St Andrews, Ctr Magnet Resonance, St Andrews KY16 9ST, Fife - Scotland

^[4] MPI Chem Energy Convers, D-45470 Mulheim - Germany

• Document type: Journal article
• Source: Helvetica Chimica Acta; v. 97, n. 6, p. 797-807, JUN 2014.
• Web of Science Citations: 5

Abstract

H-1-NMR Chemical shifts of all-syn-1,2,4,5-tetrafluorocyclohexane (1), all-syn-1,2,3,4-tetrafluorocyclohexane (2), and their complexes with benzene are calculated at the BHandH/6-311+G(2d,p) level. The observed shielding of certain resonances on going from CD2Cl2 to (D-8) toluene solution is qualitatively reproduced in these model calculations, in particular when standard B3LYP/def2-TZVP optimised geometries are employed. The results are interpreted with the quantum theory of atoms in molecules (QTAIM) and non-covalent interactions (NCI) methods, and they indicate that aromatic molecules bind strongly (1.6 kcal mol(-1)) to the `positive face' of these molecules. The level of theory is validated for the new compound all-syn-1,2,4,5-tetrafluoro-3-phenylcyclohexane (3), where a recently developed QM/MM protocol for optimisation of molecular crystals afforded excellent agreement between the B3LYP/def2-TZVP structure and that observed in the solid. (AU)

• FAPESP's process: 12/03933-5 - Conformational equilibria and intramolecular interactions for a series of amino-acids: theoretical and experimental approaches
• Grantee: Roberto Rittner Neto
• Support type: Regular Research Grants
• FAPESP's process: 11/01170-1 - Physicochemical studies of organic compounds: long range inractions and conformational analysis of organofluorine compounds.
• Grantee: Rodrigo Antonio Cormanich
• Support type: Scholarships in Brazil - Doctorate