{"title":"3/2 系统中 sp2 中心的金字塔化是与能量无关的 \"结构呼吸","authors":"Henri Brunner, Masahiro Ikeshita, Takashi Tsuno","doi":"10.1002/ejoc.202400623","DOIUrl":null,"url":null,"abstract":"In 3/2‐systems, such as the acetate anion H<jats:sub>3</jats:sub>C<jats:sub>α</jats:sub>C′OO<jats:sup>−</jats:sup>, an sp<jats:sup>3</jats:sup> center and an sp<jats:sup>2</jats:sup> center are connected by a covalent bond. The interaction of threefold and twofold symmetry results in the pyramidalization of the sp<jats:sup>2</jats:sup> center during rotation about bond E<jats:sub>sp3</jats:sub>−E<jats:sub>sp2</jats:sub>. Rotation angles <jats:italic>ψ</jats:italic>=0°, ±60°, ±120°, and ±180° account for conformations with a symmetry plane containing the planar sp<jats:sup>2</jats:sup> center C<jats:sub>α</jats:sub>C′OO. However, in all conformations with rotation angles <jats:italic>ψ</jats:italic>≠0°, ±60°, ±120°, and ±180° this symmetry plane is lost and pyramidalization must occur with maxima at rotation angles <jats:italic>ψ</jats:italic>=±30°, ±90°, and ±150°, because the two sides of the sp<jats:sup>2</jats:sup> center C<jats:sub>α</jats:sub>C′OO are different. Inevitably, this leads to a pyramidalization/rotation profile <jats:italic>θ/ψ</jats:italic> with three maxima, three minima, and six zero‐crossings. Thus, myriads of 3/2‐compounds pyramidalize their sp<jats:sup>2</jats:sup> centers each moment to the order of about 2° in a coupled pyramidalization/rotation molecular motion independent of energy.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"The Pyramidalization of sp2 Centers in 3/2‐Systems Is a “Structural Breathing” Independent of Energy\",\"authors\":\"Henri Brunner, Masahiro Ikeshita, Takashi Tsuno\",\"doi\":\"10.1002/ejoc.202400623\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"In 3/2‐systems, such as the acetate anion H<jats:sub>3</jats:sub>C<jats:sub>α</jats:sub>C′OO<jats:sup>−</jats:sup>, an sp<jats:sup>3</jats:sup> center and an sp<jats:sup>2</jats:sup> center are connected by a covalent bond. The interaction of threefold and twofold symmetry results in the pyramidalization of the sp<jats:sup>2</jats:sup> center during rotation about bond E<jats:sub>sp3</jats:sub>−E<jats:sub>sp2</jats:sub>. Rotation angles <jats:italic>ψ</jats:italic>=0°, ±60°, ±120°, and ±180° account for conformations with a symmetry plane containing the planar sp<jats:sup>2</jats:sup> center C<jats:sub>α</jats:sub>C′OO. However, in all conformations with rotation angles <jats:italic>ψ</jats:italic>≠0°, ±60°, ±120°, and ±180° this symmetry plane is lost and pyramidalization must occur with maxima at rotation angles <jats:italic>ψ</jats:italic>=±30°, ±90°, and ±150°, because the two sides of the sp<jats:sup>2</jats:sup> center C<jats:sub>α</jats:sub>C′OO are different. Inevitably, this leads to a pyramidalization/rotation profile <jats:italic>θ/ψ</jats:italic> with three maxima, three minima, and six zero‐crossings. Thus, myriads of 3/2‐compounds pyramidalize their sp<jats:sup>2</jats:sup> centers each moment to the order of about 2° in a coupled pyramidalization/rotation molecular motion independent of energy.\",\"PeriodicalId\":167,\"journal\":{\"name\":\"European Journal of Organic Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.5000,\"publicationDate\":\"2024-10-29\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"European Journal of Organic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1002/ejoc.202400623\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"European Journal of Organic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/ejoc.202400623","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
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.
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.