The C-F⋅⋅⋅H-CF2 interaction: A combination of hydrogen bonding and n → σ* stabilization

被引：5

作者：

Garrison, Nathaniel G. ^{[1
]}

Harry, Stefan Andrew ^{[1
]}

Siegler, Maxime A. ^{[1
]}

Cariello, Guilherme ^{[2
]}

Cormanich, Rodrigo A. ^{[2
]}

Lectka, Thomas ^{[1
]}

机构：

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

[2] Univ Estadual Campinas UNICAMP, Dept Quim Organ, Inst Quim, Monteiro Lobato St, BR-13083862 Campinas, SP, Brazil

来源：

JOURNAL OF FLUORINE CHEMISTRY | 2023年 / 272卷

基金：

巴西圣保罗研究基金会; 美国国家科学基金会;

关键词：

Hydrogen bonding; Tetrel bonding; Difluoromethyl H-bonding; n -> sigma* interaction; SPIN COUPLING-CONSTANTS; DENSITY-FUNCTIONAL METHODS; FLUORINE;

D O I：

10.1016/j.jfluchem.2023.110191

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

In this communication, we explore a unique molecule that exhibits a substantial interaction between a CF2H group and a CF group. In medicinal chemistry, CF2H groups are known as weak hydrogen bond donors, and CF groups as weak H-bond acceptors. Seldom are they paired up together in an array such that their unique properties can be examined. In this case, we establish that along with an attractive hydrogen bonding interaction, an n -> sigma* component anchors the interactions. A unique combination of steric and hyperconjugative effects 'switches' the interaction away from previously reported dominant tetrel-type bonding in the case of a CH2F and CF interation towards an unusualy complex hybrid interaction. Crystallographic, computational, and spectroscopic studies illuminate the problem.

引用

页数：7

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