3/2 系统中 sp2 中心的金字塔化是与能量无关的 "结构呼吸

IF 2.5 3区 化学 Q2 CHEMISTRY, ORGANIC European Journal of Organic Chemistry Pub Date : 2024-10-29 DOI:10.1002/ejoc.202400623
Henri Brunner, Masahiro Ikeshita, Takashi Tsuno
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引用次数: 0

摘要

在 3/2 系统中,如醋酸阴离子 H3CαC′OO- 中,一个 sp3 中心和一个 sp2 中心通过共价键相连。三重对称性和二重对称性的相互作用导致 sp2 中心在围绕键 Esp3-Esp2 旋转时发生金字塔化。旋转角度ψ=0°、±60°、±120°和±180°表示对称面包含平面 sp2 中心 CαC′OO 的构象。然而,在旋转角度ψ≠0°、±60°、±120°和±180°的所有构象中,这一对称平面消失了,金字塔化必须在旋转角度ψ=±30°、±90°和±150°时出现最大值,因为 sp2 中心 CαC′OO 的两侧是不同的。这不可避免地导致金字塔化/旋转曲线θ/ψ具有三个最大值、三个最小值和六个零交叉点。因此,在与能量无关的金字塔化/旋转耦合分子运动中,无数 3/2 化合物的 sp2 中心每时每刻都会发生约 2° 的金字塔化。
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The Pyramidalization of sp2 Centers in 3/2‐Systems Is a “Structural Breathing” Independent of Energy
In 3/2‐systems, such as the acetate anion H3CαC′OO, an sp3 center and an sp2 center are connected by a covalent bond. The interaction of threefold and twofold symmetry results in the pyramidalization of the sp2 center during rotation about bond Esp3−Esp2. Rotation angles ψ=0°, ±60°, ±120°, and ±180° account for conformations with a symmetry plane containing the planar sp2 center CαC′OO. However, in all conformations with rotation angles ψ≠0°, ±60°, ±120°, and ±180° this symmetry plane is lost and pyramidalization must occur with maxima at rotation angles ψ=±30°, ±90°, and ±150°, because the two sides of the sp2 center CαC′OO are different. Inevitably, this leads to a pyramidalization/rotation profile θ/ψ with three maxima, three minima, and six zero‐crossings. Thus, myriads of 3/2‐compounds pyramidalize their sp2 centers each moment to the order of about 2° in a coupled pyramidalization/rotation molecular motion independent of energy.
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来源期刊
CiteScore
5.40
自引率
3.60%
发文量
752
审稿时长
1 months
期刊介绍: The European Journal of Organic Chemistry (2019 ISI Impact Factor 2.889) publishes Full Papers, Communications, and Minireviews from the entire spectrum of synthetic organic, bioorganic and physical-organic chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. The following journals have been merged to form two leading journals, the European Journal of Organic Chemistry and the European Journal of Inorganic Chemistry: Liebigs Annalen Bulletin des Sociétés Chimiques Belges Bulletin de la Société Chimique de France Gazzetta Chimica Italiana Recueil des Travaux Chimiques des Pays-Bas Anales de Química Chimika Chronika Revista Portuguesa de Química ACH—Models in Chemistry Polish Journal of Chemistry.
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