Captodative Versus Push-Pull Aromatic Cyclopentadienyl Derivatives

IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL International Journal of Quantum Chemistry Pub Date : 2024-10-04 DOI:10.1002/qua.27490
B. A. Shainyan
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Abstract

The problem of whether and how the captodative aromatic systems with the donor and acceptor substituents at the same carbon atom of the C=C bond can be more stable than the π-conjugated push-pull counterparts with the two substituents in the vicinal position is analyzed for cyclopentadienyl derivatives possessing an aromatic cyclopentadienyl ring. The analysis of electronic, magnetic, and structural criteria of aromaticity showed that among typical organic donors, such as amines NR3, ethers R2O, guanidine (NH2)2C=NH, siloxane O(SiH3)2, silatrane, the captodative isomers [cyclopentadienylium]C(X+) = CH2 can be more stable than their push-pull isomeric counterparts [cyclopentadienylium]—CH=CH—X+. The largest energy difference in favor of the former was found to be ca. 13 kcal/mol for X = NH=C(NH2)2.

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捕获式与推拉式芳香环戊二烯衍生物
针对具有芳香环戊二烯基环的环戊二烯基衍生物,分析了供体和受体取代基位于 C=C 键同一碳原子上的俘获芳香系统是否以及如何比两个取代基位于邻位的 π 共轭推挽芳香系统更稳定的问题。对芳香性的电子、磁性和结构标准的分析表明,在典型的有机给体(如胺 NR3、醚 R2O、胍 (NH2)2C=NH、硅氧烷 O(SiH3)2、硅烷)中,俘获异构体 [cyclopentadienylium]-C(X+) = CH2 比它们的推拉异构体 [cyclopentadienylium]-CH=CH-X+ 更稳定。推拉异构体[环戊二烯]-CH=CH-X+的最大能量差约为 13 kcal/mol。13 kcal/mol。
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来源期刊
International Journal of Quantum Chemistry
International Journal of Quantum Chemistry 化学-数学跨学科应用
CiteScore
4.70
自引率
4.50%
发文量
185
审稿时长
2 months
期刊介绍: Since its first formulation quantum chemistry has provided the conceptual and terminological framework necessary to understand atoms, molecules and the condensed matter. Over the past decades synergistic advances in the methodological developments, software and hardware have transformed quantum chemistry in a truly interdisciplinary science that has expanded beyond its traditional core of molecular sciences to fields as diverse as chemistry and catalysis, biophysics, nanotechnology and material science.
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