Direct ab initio molecular dynamics study of <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" altimg="si4.gif" display="inline" overflow="scroll"><mml:mrow><mml:msubsup><mml:mrow><mml:mi mathvariant="normal">CH</mml:mi></mml:mrow><mml:mrow><mml:mn>3</mml:mn></mml:mrow><mml:mrow><mml:mo>+</mml:mo></mml:mrow></mml:msubsup><mml:mo>+</mml:mo><mml:mi mathvariant="normal">Benzene</mml:mi></mml:mrow></mml:math>

Ishikawa, Yasuyuki; Yilmaz, Hulusi; Yanai, Takeshi; Nakajima, Takahito; Hirao, Kimihiko

doi:10.1016/j.cplett.2004.07.104

Cited by 19 publications

(18 citation statements)

References 18 publications

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“…This reaction has also been taken into account extensively by Miklis and coworkers where they predicted that CH þ 3 prefers a g 1 bonding with Bz rather than g 6 bonding [11]. Different forms of the arenium ions of this reaction were investigated through an ab initio direct molecular dynamics study by Ishikawa et al [12]. These results were compared with the results obtained through Car-Parrinello molecular dynamics by Zheng et al [13].…”

Section: Introductionmentioning

confidence: 93%

On protonation and methylation of benzene: A B3LYP DFT based study

Sarkar

Shil

Paul

et al. 2009

Journal of Molecular Structure: THEOCHEM

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Section: Introductionmentioning

confidence: 93%

On protonation and methylation of benzene: A B3LYP DFT based study

Sarkar

Shil

Paul

et al. 2009

Journal of Molecular Structure: THEOCHEM

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“…[34][35][36][37][38] This information facilitates the design of biomimetic catalysts and new drugs as well as a better understanding of protein folding and function. 8,9,19,22,[39][40][41] Most of the previous studies of cation-π interactions with organic cations have used ammonium derivatives [19][20][21][22] and small cations 26,30,[42][43][44] as the probe molecule. It is known that coordinatively saturated cations interact with aromatic rings in a different manner than non-coordinatively saturated carbocations.…”

Section: Introductionmentioning

confidence: 99%

“…It is known that coordinatively saturated cations interact with aromatic rings in a different manner than non-coordinatively saturated carbocations. 26 Until presently, studies of the interaction of an aromatic ring with protons and carbocations have focused on the Friedel-Crafts alkylation mechanism, 42,43,[45][46][47][48][49][50][51][52] and the formation or characterization of π- [53][54][55][56] and σ-complexes (Scheme 1- (4)). 57, 58 The formation of both complexes is dependent on the nature of the electrophile and on the aromatic ring.…”

Section: Introductionmentioning

confidence: 99%

“…On the other hand, if the cation interacts with the aromatic π-system as a whole, located approximately at the center of the ring, it is called a η 6 complex (Scheme 1- (3)). The bonded interaction where the electrophile is added to the aromatic ring, disrupting its aromaticity, is called a σ-complex (Scheme 1-(4)).Ishikawa et al 42 studied the energetic profile by quantum molecular dynamics of the alkylation of the benzene ring by methyl cation and found that no π-complex is formed during the reaction. The interaction of the methyl cation and benzene directly affords the σ-complex.…”

mentioning

confidence: 99%

“…Ishikawa et al 42 studied the energetic profile by quantum molecular dynamics of the alkylation of the benzene ring by methyl cation and found that no π-complex is formed during the reaction. The interaction of the methyl cation and benzene directly affords the σ-complex.…”

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confidence: 99%

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Interaction of allylic carbocations with benzene: a theoretical model of carbocationic intermediates in terpene biosynthesis

Oliveira¹,

Esteves²

2011

J. Braz. Chem. Soc.

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Carbocátions atuam de formas diferentes quando interagem com anéis aromáticos. É interessante como na biosíntese de terpenos, os intermediários carbocatiônicos não alquilam a cadeia lateral aromática de aminoácidos presentes no sítio ativo, como seria esperado para outros carbocátions, como o cátion terc-butila. Neste trabalho, a interação entre benzeno e diferentes carbocátions alílicos é analisada, mimetizando carbocátions terpenóides, para melhor compreender como esta interação ocorreria. Cálculos em nível de teoria do funcional da densidade (DFT) mostram que para carbocátions alílicos secundários e terciários (como os encontrados na natureza), a forma não ligada da interação é mais estável energeticamente do que a alquilação do anel aromático, justificando a escolha da natureza por esses carbocátions mais estabilizados.Carbocations act in different ways when interacting with aromatic rings. It is interesting that in terpene biosynthesis, the carbocationic intermediates do not alkylate the aromatic side chain of the amino acids present in the enzymatic active site, as would be expected by other carbocations such as the tert-butyl cation. In this study, the interaction between benzene and different allylic carbocations, mimicking terpenoid cations, is analysed in order to better understand how this interaction would occur. Density-functional-theory (DFT) calculations show that for secondary and tertiary allylic carbocations (as found in nature), the non-covalent interaction is energetically favoured with respect to alkylation of the aromatic ring.Keywords: density-functional calculations, DFT, electrophilic substitution, cation-π interaction IntroductionThe study of noncovalent interactions has been gaining interest due to their broad applications in diverse fields such as ligand recognition, catalysis 1 and supramolecular chemistry.2 However, the importance of noncovalent interactions, such as π stacking, 3,4 charge-dipole 5,6 and cation-π interactions, 4,7-10 has only been recognized recently. A cation-π interaction is defined as a strong, attractive, noncovalent and quite specific interaction between a cation and a π-system.11 The cation-π interaction, which is of the same magnitude or even stronger than a typical hydrogen bond, 9,12 has a key role in protein folding, 13 selectivity of potassium channels 14 and several types of intermolecular recognition. 1,13,[15][16][17] The nature of the cation in the cation-π interaction can be metallic, 11,18 of ammonium derivatives, [19][20][21][22] which are very common in biological systems, 23,24 or carbocationic, 25-30 among others. Most of the available information for cation-π complexes has been obtained from coordinatively saturated cations, such as Na + and NH 4 + . 11,[18][19][20][21][22] In the case of carbocations, cation-π interactions are found as intermediates in many enzymatic reactions, e.g. elongation and cyclization reactions in terpene biosynthesis. [31][32][33] The study of the interaction of such cations with aromatic side chains of amino acids is...

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Cation–π Interactions in Graphene‐Containing Systems for Water Treatment and Beyond

2020

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was also recognized. [2] In addition to these forces, one intriguing noncovalent interaction: cation-π interaction, has emerged as an intermolecular force of great significance in chemistry, biology, and materials science. [3] The cation-π interactions basically refers to the interplay between cations and the π electron cloud of an aromatic system. It plays a great role in biological systems for molecular recognition, protein-protein interactions, and the maintenance of macromolecular structures. It also occurs in protein-ligand interactions and protein-DNA complexes. In structural biology, the positively charged amino acids interact with aromatic amino acids, which contribute to the formation of complex protein structures. The amide NHs are in close contact with the aromatic ring of another amino acid in the protein crystal structures. [4] The cation-π interactions are of great importance to protein stability. There is at least one intermolecular cation-π interaction in half of proteins and one third of homodimers, [5] making significant contributions to the tertiary and quaternary protein structures caused by protein folding. In addition, metallic cations, such as Na + , K + , Cu 2+ , Fe 2+ , Ca 2+ , exist in many enzymes. Their interactions with the π systems in protein structures cannot be ignored. In molecular neurobiology, many studies have proved that receptors bind the neurotransmitters through cation-π interactions. [6] The cation-π interaction is electrostatic in nature because the major contributions arise from the electrostatic attractions between cations and the quadrupole moment of the aromatics. [7] As a result, the strength of cation-π interactions can be the strongest among the noncovalent interactions, several times greater than others. It can also be regulated to be weak, depending on the type of cations and the nature of the π system. The adjustability of cation-π interaction offers a potential strategy to modify the neighboring environment where it is involved.Graphene, a 2D carbon network, with carbon atoms jointed together in a hexagonal honeycomb matrix, can be taken as a novel aromatic macromolecule from certain points of view. The unique structure endows it with excellent physicochemical, electronic, optical, thermal, and mechanical properties, leading to its potential applications in broad fields. [8] The interplay between cations and the delocalized polarizable π electrons of graphene, would alter the intrinsic characteristics of graphene-based structures and impart influences on the performance of graphene-based devices.Cation-π interactions are common in nature, especially in organisms. Their profound influences in chemistry, physics, and biology have been continuously investigated since they were discovered in 1981. However, the importance of cation-π interactions in materials science, regarding carbonaceous nanomaterials, has just been realized. The interplay between cations and delocalized polarizable π electrons of graphene would bring about significant changes to the intrinsic...

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Direct ab initio molecular dynamics study of CH3++Benzene

Cited by 19 publications

References 18 publications

On protonation and methylation of benzene: A B3LYP DFT based study

On protonation and methylation of benzene: A B3LYP DFT based study

Interaction of allylic carbocations with benzene: a theoretical model of carbocationic intermediates in terpene biosynthesis

Cation–π Interactions in Graphene‐Containing Systems for Water Treatment and Beyond

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