Update 1 of: Electrophilicity Index

Chattaraj, Pratim Kumar; Roy, Debesh R.

doi:10.1021/cr078014b

Cited by 583 publications

(229 citation statements)

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“…In this article we have made an attempt to study the binding of hydrogen with a host of transition metal (M) -ethylene (C 2 H 4 ) complexes [M n -(C 2 H 4 ) (M = Sc, Ti, Fe, Ni; n = 1, 2)] on the basic premise of conceptual density functional theory (CDFT) [22][23][24][25] and its various allied global reactivity descriptors like electronegativity [26][27][28] (χ), hardness [29][30][31] (η), electrophilicity [32][33][34] (ω) and the local variants like atomic charges [35] (Q k ) and Fukui functions [36] (f k ). [21] interaction between the metal atom and the interacting dihydrogen moieties.…”

Section: Introductionmentioning

confidence: 99%

Analyzing the efficiency of M n –(C2H4) (M = Sc, Ti, Fe, Ni; n = 1, 2) complexes as effective hydrogen storage materials

2011

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Abstract:Hydrogen trapping ability of various metal -ethylene complexes has been studied at the B3LYP and MP2 level of theory using the 6-311+G(d,p) basis set. Different global and local reactivity descriptors and the associated electronic structure principles provide important insights into the associated interactions. There exist two distinct classes of bonding patterns, viz., a Kubas-type interaction between the metal and the H2 molecule behaving as a η2-ligand and an electrostatic interaction between the metal and the atomic hydrogens.

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Section: Introductionmentioning

confidence: 99%

Analyzing the efficiency of M n –(C2H4) (M = Sc, Ti, Fe, Ni; n = 1, 2) complexes as effective hydrogen storage materials

2011

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“…The first four descriptors, obtained using the semiempirical AM1 methods, are molecular properties known to be useful for predicting electrophilic reactivity. [22][23][24]32,33 However, none of these molecular descriptors correlated with the k values for the dithiin−GSH reactions in a statistically significant manner (p > 0.05), suggesting that they are not suitable for the prediction of dithiin electrophilicity.…”

Section: Correlations Of Nucleophilic Susceptibility Of Dithiins Withmentioning

confidence: 97%

“…Single point energies in water were calculated for these conformers using AM1 Hamiltonian and restricted Hartree-Fock formalism on TSAR version 3.3 software (Oxford Molecular, Oxford, UK). The respective values of E HOMO and E LUMO were then used to compute the absolute difference between E HOMO and E LUMO (|E HOMO [22][23][24] Calculation of electrostatic atomic charges Q of the dithiins was performed on optimized geometries using the semi-empirical AM1 Hamiltonian method on Spartan software. Taft's polar substituent constants * obtained from the literature 25 were used for appropriate substituents of the dithiins.…”

Section: Reactivity Correlation Studiesmentioning

confidence: 99%

Chemical reactivity and biological activity of dihydro-1,4-dithiin tetraoxides

et al. 2013

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Certain dihydro-1,4-dithiin tetraoxides such as dimethipin, a commercial plant growth regulant, have been reported to exhibit highly selective biological activities depending on the type and number of substitutions on the ␣,␤-unsaturated bond in the dithiin ring. Despite the abundant reports on this class of compounds, the study of chemical reactivity of the ␣,␤-unsaturated bond in the dithiin ring has not been reported and the factors governing the biological selectivity of these compounds are still unknown. In this study, the reactivity of eight dithiin compounds substituted in varying degrees at the ␣,␤-unsaturated bond towards biologically important nucleophilic groups at pH 7.4 were investigated using UV-vis, fluorescence, and 1 H NMR spectroscopies. Their reactivity towards glutathione correlated strongly with their cell growth inhibitory activity and inhibition of DNA topoisomerase II, an enzyme containing critical sulfhydryl groups. On this basis, the mechanism by which these dithiins achieve the biological selectivity previously reported was proposed. Excellent correlations between glutathione reactivity and Taft's polar substituent constants or electrostatic atomic charges of the dithiins were also demonstrated, suggesting that these descriptors might be useful for predicting the reactivity of other dithiins towards sulfhydryl nucleophiles.Key words: dithiins, dimethipin, herbicides, plant growth regulants, microbicides, sulfhydryl binding, reactivity, topoisomerase II, cell growth inhibition, QSAR.Résumé : On a signalé que certains tétraoxydes de dihydro-1,4-dithiine, dont la diméthipine, un régulateur de croissance végétale du commerce, présentent une activité biologique hautement sélective qui dépend du type et du nombre de substitutions sur la liaison ␣,␤-non saturée dans le noyau dithiine. Malgré les nombreux rapports ayant trait à cette classe de composés, aucune étude de la réactivité chimique de la liaison ␣,␤-non saturée dans le noyau dithiine n'a été décrite et les facteurs qui régissent la sélectivité biologique de ces composés demeurent inconnus. Dans la présente étude, on explore la réactivité de huit composés de la dithiine substitués à divers degrés sur la liaison ␣,␤-non saturée vis à vis de groupes nucléophiles importants du point de vue biologique à pH 7,4 par spectrométrie UV vis, de fluorescence et RMN de 1 H. Leur réactivité vis à vis du glutathion était fortement corrélée à leur activité d'inhibition de la croissance cellulaire et à l'inhibition de la topoisomérase II de l'ADN, un enzyme contenant des groupements sulfhydryles critiques. Ces constatations ont permis de proposer le mécanisme grâce auquel ces dithiines manifestent la sélectivité biologique signalée antérieurement. On a aussi montré l'existence d'excellentes corré-lations entre la réactivité du glutathion et les constantes polaires de Taft ou les charges électrostatiques atomiques des dithiines, ce qui donnent à penser que ces descripteurs pourraient être utiles pour prédire la réactivité d'autres dithiines ...

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“…On the other hand, to calculate the reactivity descriptors the MolReactivity program, version 1.0 (2014) made by our research group [136][137][138][139][140], was used, taking into account (1)- (18), in order to characterize the interaction energy from closed-shell (steric) repulsion, CT from occupied-vacant orbital interactions, and polarization effects, among other reaction parameters. Finally, the MPWB1K hybrid metafunctional was used due to that it is a general functional that includes covalent, partial (TS), hydrogen, and weak bonds.…”

Section: Computational Detailsmentioning

confidence: 99%

Understanding the Polar Character Trend in a Series of Diels-Alder Reactions Using Molecular Quantum Similarity and Chemical Reactivity Descriptors

Morales-Bayuelo

Vivas‐Reyes

2014

Journal of Quantum Chemistry

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In molecular similarity there is a premise "similar molecules tend to behave similarly"; however in the actual quantum similarity field there is no clear methodology to describe the similarity in chemical reactivity, and with this end an analysis of charge-transfer (CT) processes in a series of Diels-Alder (DA) reactions between cyclopentadiene (Cp) and cyano substitutions on ethylene has been studied. The CT analysis is performed in the reagent assuming a grand canonical ensemble and the considerations for an electrophilic system using B3LYP/6-31 ( ) and M06-2X/6-311 + ( , ) methods. An analysis for CT was performed in agreement with the experimental results with a good statistical correlation ( 2 = 0.9118) relating the polar character to the bond force constants in DA reactions. The quantum distortion analysis on the transition states (TS) was performed using molecular quantum similarity indexes of overlap and coulomb showing good correlation ( 2 = 0.8330) between the rate constants and quantum similarity indexes. In this sense, an electronic reorganization based on molecular polarization in terms of CT is proposed; therefore, new interpretations on the electronic systematization of the DA reactions are presented, taking into account that today such electronic systematization is an open problem in organic physical chemistry. Additionally, one way to quantify the similarity in chemical reactivity was shown, taking into account the dependence of the molecular alignment on properties when their position changes; in this sense a possible way to quantify the similarity of the CT in systematic form on these DA cycloadditions was shown.

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Update 1 of: Electrophilicity Index

Cited by 583 publications

References 397 publications

Analyzing the efficiency of M n –(C2H4) (M = Sc, Ti, Fe, Ni; n = 1, 2) complexes as effective hydrogen storage materials

Analyzing the efficiency of M n –(C2H4) (M = Sc, Ti, Fe, Ni; n = 1, 2) complexes as effective hydrogen storage materials

Chemical reactivity and biological activity of dihydro-1,4-dithiin tetraoxides

Understanding the Polar Character Trend in a Series of Diels-Alder Reactions Using Molecular Quantum Similarity and Chemical Reactivity Descriptors

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