Density functional study of interactions between fluorinated cyclohexanes and arenes
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1H-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 (D8)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.
Cormanich , R A , Durie , A , Bjornsson , R , Rittner , R , O'Hagan , D & Buehl , M 2014 , ' Density functional study of interactions between fluorinated cyclohexanes and arenes ' , Helvetica Chimica Acta , vol. 97 , no. 6 , pp. 797-807 . https://doi.org/10.1002/hlca.201400049
Helvetica Chimica Acta
Copyright © 2014 Verlag Helvetica Chimica Acta AG, Zürich. This is the accepted version of the following article: Cormanich, R. A., Durie, A., Bjornsson, R., Rittner, R., O'Hagan, D. and Bühl, M. (2014), Density Functional Study of Interactions between Fluorinated Cyclohexanes and Arenes. HCA, 97: 797–807., which has been published in final form at http://dx.doi.org/10.1002/hlca.201400049
DescriptionThe authors thank a Grant # 2012/03933-5, Sao Paulo Research Foundation (FAPESP), for providing financial support for this research, for a scholarship (to R.A.C. #2011/01170-1, FAPESP). CNPq is also acknowledged for a fellowship (to R.R) and a studentship (to R.A.C.). We thank the Royal Society (Wolfson Merit Award for D.O' H.) and EaStCHEM (support for M.B. and access to a computing facility maintained by H. Fruchtl).
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