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Stabilization of 2,6-Diarylanilinum Cation by Through-Space Cation-pi Interactions

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Energetically favorable cation-pi interactions play important roles in numerous molecular recognition processes in chemistry and biology. Herein, we present synergistic experimental and computational physical organic chemistry studies on 2,6-diarylanilines that contain flanking meta/parasubstituted aromatic rings adjacent to the central anilinium ion. A combination of measurements of pK(a) values, structural analyses of 2,6-diarylanilinium cations, and quantum chemical analyses based on the quantitative molecular orbital theory and a canonical energy decomposition analysis (EDA) scheme reveal that through-space cation-pi interactions essentially contribute to observed trends in proton affinities and pK(a) values of 2,6-diarylanilines.

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PADIAL, Joan simó, POATER I TEIXIDOR, Jordi, NGUYEN, D. thao, TINNEMANS, Paul, BICKELHAUPT, F. matthias, MECINOVIĆ, Jasmin. Stabilization of 2,6-Diarylanilinum Cation by Through-Space Cation-pi Interactions. _Journal of Organic Chemistry_. 2017. Vol. 82, núm. 18, pàgs. 9418-9424. [consulta: 25 de gener de 2026]. ISSN: 0022-3263. [Disponible a: https://hdl.handle.net/2445/127932]

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