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

Joan Simó Padial; Jordi Poater; D. Thao Nguyen; Paul Tinnemans; F. Matthias Bickelhaupt; Jasmin Mecinović

doi:10.1021/acs.joc.7b01406

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

Joan Simó Padial
, Jordi Poater
, D. Thao Nguyen
, Paul Tinnemans
, F. Matthias Bickelhaupt^*
, Jasmin Mecinović

^*Corresponding author for this work

AIMMS

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

Energetically favorable cation-π 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/para-substituted 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-π interactions essentially contribute to observed trends in proton affinities and pK_a values of 2,6-diarylanilines.

Original language	English
Pages (from-to)	9418-9424
Number of pages	7
Journal	Journal of Organic Chemistry
Volume	82
Issue number	18
DOIs	https://doi.org/10.1021/acs.joc.7b01406
Publication status	Published - 15 Sept 2017

Funding

We thank The Netherlands Organization for Scientific Research (NWO) for financial support. J.P. thanks the Spanish MINECO (CTQ2016-77558-R).

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???publication-publication-funding-organisation-not-added???	08010

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10.1021/acs.joc.7b01406

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title = "Stabilization of 2,6-Diarylanilinum Cation by Through-Space Cation-π Interactions",

abstract = "Energetically favorable cation-π 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/para-substituted aromatic rings adjacent to the central anilinium ion. A combination of measurements of pKa 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-π interactions essentially contribute to observed trends in proton affinities and pKa values of 2,6-diarylanilines.",

author = "\{Sim{\'o} Padial\}, Joan and Jordi Poater and Nguyen, \{D. Thao\} and Paul Tinnemans and Bickelhaupt, \{F. Matthias\} and Jasmin Mecinovi{\'c}",

year = "2017",

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doi = "10.1021/acs.joc.7b01406",

language = "English",

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T1 - Stabilization of 2,6-Diarylanilinum Cation by Through-Space Cation-π Interactions

AU - Simó Padial, Joan

AU - Poater, Jordi

AU - Nguyen, D. Thao

AU - Tinnemans, Paul

AU - Bickelhaupt, F. Matthias

AU - Mecinović, Jasmin

PY - 2017/9/15

Y1 - 2017/9/15

N2 - Energetically favorable cation-π 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/para-substituted aromatic rings adjacent to the central anilinium ion. A combination of measurements of pKa 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-π interactions essentially contribute to observed trends in proton affinities and pKa values of 2,6-diarylanilines.

AB - Energetically favorable cation-π 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/para-substituted aromatic rings adjacent to the central anilinium ion. A combination of measurements of pKa 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-π interactions essentially contribute to observed trends in proton affinities and pKa values of 2,6-diarylanilines.

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DO - 10.1021/acs.joc.7b01406

M3 - Article

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VL - 82

SP - 9418

EP - 9424

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 18

ER -

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

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CCDC 1545154: Experimental Crystal Structure Determination

CCDC 1545155: Experimental Crystal Structure Determination

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

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CCDC 1545154: Experimental Crystal Structure Determination

CCDC 1545155: Experimental Crystal Structure Determination

Cite this