Intra- and Intermolecular Cation–π Interactions between Onium Salts and Alkynes/Acetylene: Experimental and Theoretical Insights,The Journal of Organic Chemistry

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Intra- and Intermolecular Cation–π Interactions between Onium Salts and Alkynes/Acetylene: Experimental and Theoretical Insights
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2023-10-11 , DOI: 10.1021/acs.joc.3c01514
Catherine Fressigné ₁ , Alexandre Jean _{1,

2} , Morgane Sanselme ₃ , Jérôme Blanchet ₂ , Jacques Rouden ₂ , Jacques Maddaluno ₁ , Michaël De Paolis ₁

Affiliation

Cation–π interactions between various onium salts, alkynes, and acetylene were studied, taking into account the substituents of the triple bond, the nature of the anions, and the polarity of the solvent, through a combination of MP2 calculations and experiments. In an intramolecular setting, these data (including single-crystal X-ray crystallography) concurred with the stability of folded conformers of alkynyl onium salts, even substituted with electron-withdrawing groups. To examine the contribution of these interactions on the alkyne electronic population, a thorough in silico study was carried out using natural bonding orbital analysis of the conformers. Intramolecular interactions from sulfonium salt tethered to phenylalkyne were highlighted, as illustrated above by the computed folded conformation (MP2) along with noncovalent interaction (NCI) analysis. Furthermore, investigations of intermolecular interactions, involving acetylene or phenylacetylene with various onium ions, revealed the high energy interactions of their complexes with phenyldimethylsulfonium chloride, as illustrated above with the complex PhC≡CH/PhMe₂SCl (MP2 calculations and NCI analysis).

中文翻译：

鎓盐与炔烃/乙炔之间的分子内和分子间阳离子-π相互作用：实验和理论见解

通过MP2计算和实验相结合，考虑到三键的取代基、阴离子的性质和溶剂的极性，研究了各种鎓盐、炔烃和乙炔之间的阳离子-π相互作用。在分子内环境中，这些数据（包括单晶 X 射线晶体学）与炔基鎓盐折叠构象异构体的稳定性一致，甚至被吸电子基团取代。为了研究这些相互作用对炔电子群体的贡献，利用构象异构体的自然键合轨道分析进行了彻底的计算机研究。如上通过计算的折叠构象 (MP2) 以及非共价相互作用 (NCI) 分析所示，突出显示了与苯炔相连的锍盐的分子内相互作用。此外，涉及乙炔或苯乙炔与各种鎓离子的分子间相互作用的研究揭示了它们的络合物与氯化苯基二甲基锍的高能相互作用，如上面用络合物PhC≡CH/PhMe 2 SCl所说明的（MP2计算和NCI分析_）。

更新日期：2023-10-11

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