The close interaction of a C-F bond with a carbonyl π-system: Attractive, repulsive, or both?

被引：11

作者：

Holl, Maxwell Gargiulo ^{[1
]}

Struble, Mark D. ^{[1
]}

Siegler, Maxime A. ^{[1
]}

Lectka, Thomas ^{[1
]}

机构：

[1] Johns Hopkins Univ, Dept Chem, New Chem Bldg,3400 North Charles St, Baltimore, MD 21218 USA

来源：

JOURNAL OF FLUORINE CHEMISTRY | 2016年 / 188卷

基金：

美国国家科学基金会;

关键词：

Physical organic; Noncovalent interactions; Electron deformation density; CENTER-DOT-F; FLUORINE; DENSITY; SEARCH;

D O I：

10.1016/j.jfluchem.2016.06.016

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

We have synthesized a molecule containing a close interaction between a C-F bond and the pi-orbitals of a ketone carbonyl group. Our studies have revealed that there is a combination of attractive and repulsive forces at play: the ketone's IR stretching mode is blue-shifted, the carbonyl is bent away from the fluorine atom, and electron deformation density maps show some significant distortion of the fluorine atom's electron density distribution. Finally, binding of the ketone to an aluminum-based Lewis acid deshields the fluorine nucleus. IR and NMR spectroscopy, single crystal X-ray crystallography, and quantum mechanical calculations were used to investigate this unusual interaction. (C) 2016 Elsevier B.V. All rights reserved.

引用

页码：126 / 130

页数：5

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