Interaction between some anions and deficient olefinic and aromatic centers

Ebrahimi, Ali; Habibi, Mostafa; Sayyadi, Omid

doi:10.1016/j.theochem.2008.03.002

Cited by 6 publications

(4 citation statements)

References 29 publications

(36 reference statements)

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“…During the AP ? interaction, as expected, [61] the anti-bonding orbitals of the CAC bonds of the electrondeficient aromatic ring (p-type orbitals of the C atoms) are filled by lone-pair electrons of the anion. In contrast, the CP k interaction occurs between the overlapping (both s-and ptype) lone pairs of the F atoms of hexafluoro-benzene and the vacant valence-shell orbitals of the cation.…”

Section: Electron-deficient Aromatic Ringssupporting

confidence: 79%

Four faces of the interaction between ions and aromatic rings

et al. 2017

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Non-covalent interactions between ions and aromatic rings play an important role in the stabilization of macromolecular complexes; of particular interest are peptides and proteins containing aromatic side chains (Phe, Trp, and Tyr) interacting with negatively (Asp and Glu) and positively (Arg and Lys) charged amino acid residues. The structures of the ion-aromatic-ring complexes are the result of an interaction between the large quadrupole moment of the ring and the charge of the ion. Four attractive interaction types are proposed to be distinguished based on the position of the ion with respect to the plane of the ring: perpendicular cation-π (CP ), co-planar cation-π (CP ), perpendicular anion-π (AP ), and co-planar anion-π (AP ). To understand more than the basic features of these four interaction types, a systematic, high-level quantum chemical study is performed, using the X + C H , M + C H , X + C F , and M + C F model systems with X = H , F , Cl , HCOO , CH COO and M = H , Li , Na , NH4+, CH NH3+, whereby C H and C F represent an electron-rich and an electron-deficient π system, respectively. Benchmark-quality interaction energies with small uncertainties, obtained via the so-called focal-point analysis (FPA) technique, are reported for the four interaction types. The computations reveal that the interactions lead to significant stabilization, and that the interaction energy order, given in kcal mol in parentheses, is CP (23-37) > AP (14-21) > CP (9-22) > AP (6-16). A natural bond orbital analysis performed leads to a deeper qualitative understanding of the four interaction types. To facilitate the future quantum chemical characterization of ion-aromatic-ring interactions in large biomolecules, the performance of three density functional theory methods, B3LYP, BHandHLYP, and M06-2X, is tested against the FPA benchmarks, with the result that the M06-2X functional performs best. © 2017 Wiley Periodicals, Inc.

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Section: Electron-deficient Aromatic Ringssupporting

confidence: 79%

Four faces of the interaction between ions and aromatic rings

et al. 2017

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“…They located minima for anion–centroid bonding, but also for σ complexes, π stacking (N 3 − ), and hydrogen‐bonding geometries 286. For F − , a strongly covalent binding mode (Figure 28 c) has been observed in many calculation studies,275b, 278, 284a, 286, 287 in agreement with the covalent bonding of F − to hexafluorobenzene observed in the gas phase 281. However, calculations showed that increasing solvation of the anion drives the binding preferably towards the geometries with more anion–π character (Figure 28 b,d).…”

Section: Anion–π Interactionsmentioning

confidence: 85%

“…Since then, numerous calculations have emerged on anions in complex with various aromatic systems,284b, 287, 290 and on the cooperativity of the anion–π interaction with other noncovalent interactions 209b,c. 291 The total interaction energies of anion–π complexes have been calculated to be comparable284b or smaller28 than those of cation–π complexes: because of the greater size of anions compared to cations, the interaction partners have to be further apart from each other, resulting in reduced electrostatic interaction.…”

Section: Anion–π Interactionsmentioning

confidence: 99%

Aromatic Rings in Chemical and Biological Recognition: Energetics and Structures

2011

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This review describes a multidimensional treatment of molecular recognition phenomena involving aromatic rings in chemical and biological systems. It summarizes new results reported since the appearance of an earlier review in 2003 in host-guest chemistry, biological affinity assays and biostructural analysis, data base mining in the Cambridge Structural Database (CSD) and the Protein Data Bank (PDB), and advanced computational studies. Topics addressed are arene-arene, perfluoroarene-arene, S⋅⋅⋅aromatic, cation-π, and anion-π interactions, as well as hydrogen bonding to π systems. The generated knowledge benefits, in particular, structure-based hit-to-lead development and lead optimization both in the pharmaceutical and in the crop protection industry. It equally facilitates the development of new advanced materials and supramolecular systems, and should inspire further utilization of interactions with aromatic rings to control the stereochemical outcome of synthetic transformations.

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“…Seither sind zahlreiche Berechnungen von Anionen im Komplex mit verschiedenen aromatischen Systemen [284b, 287,290] sowie im Bezug auf die Kooperativität der Anion-p-mit anderen nichtkovalenten Wechselwirkungen erschienen. [209b,c, 291] Die totalen Wechselwirkungsenergien der Anion-p-Komplexe wurden als vergleichbar [284b] oder kleiner [28] Die Bindungsenergien wurden als proportional ansteigend zur Zahl der mit dem Anion interagierenden, elektronenarmen Arene berechnet: 1:2-Cl À /Br À ···(Trifluortriazin) 2 -Komplexe zeigten Bindungsenergien von ungefähr zwei-und die 1:3-Komplexe von dreifacher Stärke des 1:1-Komplexes.…”

Section: Aromatische Ringeunclassified

Aromatische Ringe in chemischer und biologischer Erkennung: Energien und Strukturen

2011

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Dieser Aufsatz beschreibt Phänomene der molekularen Erkennung von aromatischen Ringen in chemischen und biologischen Systemen in einem multidimensionalen Ansatz. Neue Ergebnisse aus der Wirt‐Gast‐Chemie, biologischen Affinitätsassays und Biostrukturanalysen, Datenbanksuchen in der Cambridge Structural Database (CSD) und der Protein Data Bank (PDB) und hochentwickelten Rechnungen, die seit dem Erscheinen eines früheren Aufsatzes in 2003 veröffentlicht wurden, sind hier zusammengefasst. Die Themen Aren‐Aren‐, Perfluoraren‐Aren‐, Schwefel‐Aren‐, Kation‐π‐ und Anion‐π‐Wechselwirkungen sowie Wasserstoffbrücken zu aromatischen Systemen werden behandelt. Das gewonnene Wissen kommt besonders der strukturbasierten Hit‐zur‐Leitstruktur‐Entwicklung und der Leitstrukturoptimierung sowohl in der pharmazeutischen als auch in der Pflanzenschutzindustrie zugute. Zudem erleichtert es die Entwicklung neuer Materialien und supramolekularer Systeme und soll zu weiteren Anwendungen von Wechselwirkungen mit aromatischen Ringen zur Kontrolle des stereochemischen Verlaufs chemischer Umsetzungen inspirieren.

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Interaction between some anions and deficient olefinic and aromatic centers

Cited by 6 publications

References 29 publications

Four faces of the interaction between ions and aromatic rings

Four faces of the interaction between ions and aromatic rings

Aromatic Rings in Chemical and Biological Recognition: Energetics and Structures

Aromatische Ringe in chemischer und biologischer Erkennung: Energien und Strukturen

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