On substituent effect in 1,n–homodisubstituted polyenes

IF 2.1 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY
Marek Graff, Sawomir Ostrowski, Jan Cz. Dobrowolski
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Abstract

The all-trans and all-cis polyenes homodisubstituted at the ends were calculated at the B3LYP/6-31G** level. The disubstitution gives rise to three end-types of the conformers: trans-trans, trans-cis, and cis-cis, denoted as EE, EZ, and ZZ. The symmetry of the EE or ZZ all-cis isomers depended on the double bond parity. Twelve substituents used: H, BeH, BH2, BF2, Br, CH3, Cl, CN, F, NH2, NO2, OH, and SiH3 were chosen to exhibit different σ- and π-electron donating and electron withdrawing properties. For polyenes composed up to ca. 20 C-atoms, the π-electron donating and withdrawing character of the end groups matters and differently acting substituents play significantly different roles. Unexpectedly, the intramolecular interactions between the substituents and the neighboring chain CH groups near appeared more decisive for the compound’s stability than the substituent electron donating/withdrawing properties. The substituent-chain interplay was consonant in the all-trans and all-cis polyenes. Still, they were always more destabilizing in the latter than in all-trans isomers.

Abstract Image

1,n-homodisubstituted polyenes 中的取代基效应
在 B3LYP/6-31G** 水平上计算了端部同源二取代的全反式和全顺式多烯。二取代产生了三种末端类型的构象:反式-反式、反式-顺式和顺式-顺式,分别称为 EE、EZ 和 ZZ。EE 或 ZZ 全顺式异构体的对称性取决于双键的奇偶性。使用了 12 个取代基:选择 H、BeH、BH2、BF2、Br、CH3、Cl、CN、F、NH2、NO2、OH 和 SiH3 这十二个取代基是为了显示不同的 σ- 和 π-电子捐赠和电子收回特性。对于由多达约 20 个 C 原子组成的多烯烃,端基的 π 电子捐献和汲取特性非常重要,不同作用的取代基发挥着显著不同的作用。出乎意料的是,取代基与邻近链 CH 基团之间的分子内相互作用比取代基的供电子/抽电子特性对化合物的稳定性更具决定性。在全反式和全顺式多烯中,取代基链之间的相互作用是一致的。不过,与全反式异构体相比,全顺式多烯烃中取代基链的不稳定性更高。
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来源期刊
Structural Chemistry
Structural Chemistry 化学-化学综合
CiteScore
3.80
自引率
11.80%
发文量
227
审稿时长
3.7 months
期刊介绍: Structural Chemistry is an international forum for the publication of peer-reviewed original research papers that cover the condensed and gaseous states of matter and involve numerous techniques for the determination of structure and energetics, their results, and the conclusions derived from these studies. The journal overcomes the unnatural separation in the current literature among the areas of structure determination, energetics, and applications, as well as builds a bridge to other chemical disciplines. Ist comprehensive coverage encompasses broad discussion of results, observation of relationships among various properties, and the description and application of structure and energy information in all domains of chemistry. We welcome the broadest range of accounts of research in structural chemistry involving the discussion of methodologies and structures,experimental, theoretical, and computational, and their combinations. We encourage discussions of structural information collected for their chemicaland biological significance.
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