Morphing the Internal Dynamics of Acetylacetone by CH3 → CF3 Substitutions. The Rotational Spectrum of Trifluoroacetylacetone

被引：12

作者：

Favero, Laura B. ^{[1
]}

Evangelisti, Luca ^{[2
]}

Velino, Biagio ^{[2
]}

Caminati, Walther ^{[2
]}

机构：

[1] CNR, ISMN, Sez Bologna, I-40129 Bologna, Italy

[2] Univ Bologna, Dipartimento Chim G Ciamician, I-40126 Bologna, Italy

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2014年 / 118卷 / 24期

关键词：

PI-ELECTRON DELOCALIZATION; GAS-PHASE; AB-INITIO; MOLECULAR-STRUCTURE; MICROWAVE-SPECTRUM; BETA-DIKETONES; SPECTROSCOPY; CONFORMERS; BRIDGES; FORMS;

D O I：

10.1021/jp5005727

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The rotational spectrum of trifluoroacetylacetone shows that the molecule exists in an enolic C-s form and displays the features of internal rotations of the CH3 and CF3 groups, whose barriers to internal rotation were determined to be V-3 = 379 and 30.8 cm(-1), respectively. Its internal dynamics appears to be intermediate between those of acetylacetone, where proton tunneling and low-barrier internal rotation of the two methyl groups make the spectrum quite complex, and hexafluoroacetylacetone, a perfectly "rigid" molecule on the time scale of microwave spectroscopy.

引用

页码：4243 / 4248

页数：6

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