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Density Functional Study of Interactions between Fluorinated Cyclohexanes and Arenes
Author(s) -
Cormanich Rodrigo A.,
Durie Alastair,
Bjornsson Ragnar,
Rittner Roberto,
O'Hagan David,
Bühl Michael
Publication year - 2014
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.201400049
Subject(s) - chemistry , cyclohexanes , molecule , benzene , density functional theory , toluene , computational chemistry , atoms in molecules , aromaticity , crystallography , stereochemistry , organic chemistry
1 H‐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 CD 2 Cl 2 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.