Density Functional Study of Interactions between Fluorinated Cyclohexanes and Arenes

被引：4

作者：

Cormanich, Rodrigo A. ^{[1
,2
,3
]}

Durie, Alastair ^{[1
,2
]}

Bjornsson, Ragnar ^{[4
]}

Rittner, Roberto ^{[3
]}

O'Hagan, David ^{[1
,2
]}

Buehl, Michael ^{[1
,2
]}

机构：

[1] Univ St Andrews, EastChem Sch Chem, St Andrews KY16 9ST, Fife, Scotland

[2] Univ St Andrews, Ctr Magnet Resonance, St Andrews KY16 9ST, Fife, Scotland

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

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

来源：

HELVETICA CHIMICA ACTA | 2014年 / 97卷 / 06期

基金：

巴西圣保罗研究基金会; 英国工程与自然科学研究理事会;

关键词：

INTERMOLECULAR INTERACTIONS; DESIGN;

D O I：

10.1002/hlca.201400049

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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.

引用

页码：797 / 807

页数：11

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