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

Sarkar, Sonali; Shil, Suranjan; Paul, S.; Misra, Anirban

doi:10.1016/j.theochem.2009.09.026

Cited by 4 publications

(3 citation statements)

References 24 publications

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“…The Gaussian 09 program and B3LYP/6-31G method were used to optimize the structure of the APDI molecule, and the atomic polar tensor charge was calculated and molecular orbital analysis was performed (Figure S5). The atomic charge can be used to predict the reaction site of the molecule . From the perspective of electrostatic interactions, the atom with more negative charge is more likely to be attacked by electrophilic reagents, such as ·OH.…”

Section: Results and Discussionmentioning

confidence: 99%

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Transient Chemiluminescence Assay for Real-Time Monitoring of the Processes of SO₃^2–-Based Advanced Oxidation Reactions

Sun

Song

Xie

et al. 2022

Environ. Sci. Technol.

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The hydroxyl radical (·OH) is a strong oxidizing agent in situ generated in advanced oxidation processes (AOPs) and crucial for assessing the performances of AOPs toward organic contaminants’ degradation. Herein, we developed a specific luminescent probe, APDI (N′ N′-di(propylethylenediamine)-perylene-3,4,9,10-tetracarboxylic diimide), to selectively detect ·OH among diverse reactive oxygen species and other radicals. Based on the transient chemiluminescence (TCL) spectra, the in situ concentration profile of ·OH within 0.01 s interval time in classical Fenton reactions and four kinds of SO3 2–-based AOPs was obtained, which provides insights into the high dynamic processes of the whole ·OH generation and consumption processes. Besides, compared with acidic conditions, reduced degradation efficiencies in Fe2+–SO3 2– and Fe2+–SO3 2––H2O2 systems were found under neutral conditions. The complete depletion of active free radicals due to SO2 –̇ radicals generated from Fe2+ and SO3 2– should account most for decreased degradation efficiencies evidenced by a new SO2* TCL signal discovered in the TCL spectra. In addition, similar phenomena have also been found in other M(n–1)+–SO3 2–-related AOPs. As SO3 2– and HSO3 – often exist naturally in wastewater, more efforts are needed to improve the performance of Fe2+–H2O2 systems. This discovery has important significance for organic contaminant degradation in a natural environment.

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Section: Results and Discussionmentioning

confidence: 99%

“…The atomic charge can be used to predict the reaction site of the molecule. 39 From the perspective of electrostatic interactions, the atom with more negative charge is more likely to be attacked by electrophilic reagents, such as •OH. It could be seen from the results that the C atoms on the carbon chain (position A shown in Figures 2 and S5…”

Section: Resultsmentioning

confidence: 99%

Transient Chemiluminescence Assay for Real-Time Monitoring of the Processes of SO₃^2–-Based Advanced Oxidation Reactions

Sun

Song

Xie

et al. 2022

Environ. Sci. Technol.

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“…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%

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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Quantum chemical studies on chameleonic ligand and its grid-type copper(I) and zinc(II) complexes

Patroniak

Markiewicz

Hoffmann

2010

Journal of Molecular Structure: THEOCHEM

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

Cited by 4 publications

References 24 publications

Transient Chemiluminescence Assay for Real-Time Monitoring of the Processes of SO₃^2–-Based Advanced Oxidation Reactions

Transient Chemiluminescence Assay for Real-Time Monitoring of the Processes of SO₃^2–-Based Advanced Oxidation Reactions

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

Quantum chemical studies on chameleonic ligand and its grid-type copper(I) and zinc(II) complexes

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

Cited by 4 publications

References 24 publications

Transient Chemiluminescence Assay for Real-Time Monitoring of the Processes of SO32–-Based Advanced Oxidation Reactions

Transient Chemiluminescence Assay for Real-Time Monitoring of the Processes of SO32–-Based Advanced Oxidation Reactions

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

Quantum chemical studies on chameleonic ligand and its grid-type copper(I) and zinc(II) complexes

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Product

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Transient Chemiluminescence Assay for Real-Time Monitoring of the Processes of SO₃^2–-Based Advanced Oxidation Reactions

Transient Chemiluminescence Assay for Real-Time Monitoring of the Processes of SO₃^2–-Based Advanced Oxidation Reactions