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Density Functional Theory and Reactivity Indices: Applications in Organic Chemical Reactivity

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Computational and Theoretical Chemistry".

Deadline for manuscript submissions: closed (30 November 2016) | Viewed by 60054

Special Issue Editors


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Guest Editor
Department of Organic Chemistry, University of Valencia, Dr. Moliner 50, Burjassot, 46100 Valencia, Spain
Interests: molecular electron density theory (MEDT); theoretical organic chemistry; chemical concepts; structure and reactivity; molecular mechanisms and selectivities; quantum-chemical topology
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Istituto di Scienze e Tecnologie Chimiche "Giulio Natta" - SCITEC, Consiglio Nazionale delle Ricerche, via C. Golgi 19, 20133 Milano, Italy
Interests: Density Functional Theory; post-SCF methods; chemical reactivity; catalysis
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

In order to emphasise the idea that the capability for changes in electron density, and not molecular orbital interactions, are responsible for the molecular reactivity in organic chemistry, a new reactivity theory, named Molecular Electron Density Theory (MEDT), is being proposed. Within the MEDT, the molecular reactivity in organic chemistry is studied using quantum chemical tools based on the analysis of the electron density such as the conceptual Density Functional Theory (DFT) reactivity indices, the topological analysis of the Electron Localisation Function (ELF) of the electron density focused on the progress of the bonding changes along the reaction path and the non-covalent interactions (NCI) analysis at the transition state structures (TSs) in order to understand experimental outcomes.

Conceptual DFT—a branch of DFT developed in the last quarter of the last century—provided rigorous theoretical tools to justify and deeply understand chemical concepts (such as electronegativity and the HSAB principle) which have been known and used by chemists for many years. In this framework, global and local reactivity indices were also defined, usually as derivatives of the molecular electron density and energy.

Since the beginning of this century, the analysis of the global DFT reactivity indices, such as the electronic chemical potential µ, the chemical hardness η, the electrophilicity ω and the nucleophilicity N, and the analysis of the local indices, such as local softness and Parr functions, have proved to be a powerful tool in the study of reactivity and selectivity (regio- and chemoselectivity) in polar organic reactions.

In this Special Issue, several studies in which the analysis of the DFT reactivity indices of the reagents involved in organic reactions provides meaningful information are presented, thus reflecting the broad range of applications of DFT indices in the study of organic chemical reactivity.

Prof. Dr. Luis R. Domingo
Dr. Alessandro Ponti
Guest Editors

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Keywords

  • DFT reactivity indices
  • electronic chemical potential
  • chemical hardness and softness
  • global and local reactivity indices
  • electrophilicity
  • nucleophilicity
  • Fukui functions
  • Parr functions
  • HSAB principle
  • organic Reactions
  • reactivity
  • regioselectivity
  • chemoselectivity
  • solvent effects

Published Papers (9 papers)

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Research

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3211 KiB  
Article
Theoretical Reactivity Study of Indol-4-Ones and Their Correlation with Antifungal Activity
by María De los Ángeles Zermeño-Macías, Marco Martín González-Chávez, Francisco Méndez, Rodolfo González-Chávez and Arlette Richaud
Molecules 2017, 22(3), 427; https://doi.org/10.3390/molecules22030427 - 08 Mar 2017
Cited by 13 | Viewed by 4441
Abstract
Chemical reactivity descriptors of indol-4-ones obtained via density functional theory (DFT) and hard–soft acid–base (HSAB) principle were calculated to prove their contribution in antifungal activity [...] Full article
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1030 KiB  
Article
The Nitrilimine–Alkene Cycloaddition Regioselectivity Rationalized by Density Functional Theory Reactivity Indices
by Giorgio Molteni and Alessandro Ponti
Molecules 2017, 22(2), 202; https://doi.org/10.3390/molecules22020202 - 26 Jan 2017
Cited by 14 | Viewed by 5004
Abstract
Conventional frontier molecular orbital theory is not able to satisfactorily explain the regioselectivity outcome of the nitrilimine–alkene cycloaddition. We considered that conceptual density functional theory (DFT) could be an effective theoretical framework to rationalize the regioselectivity of the title reaction. Several nitrilimine–alkene cycloadditions [...] Read more.
Conventional frontier molecular orbital theory is not able to satisfactorily explain the regioselectivity outcome of the nitrilimine–alkene cycloaddition. We considered that conceptual density functional theory (DFT) could be an effective theoretical framework to rationalize the regioselectivity of the title reaction. Several nitrilimine–alkene cycloadditions were analyzed, for which we could find regioselectivity data in the literature. We computed DFT reactivity indices at the B3LYP/6-311G(2d,p)//B3LYP/6-31G(d,p) and employed the grand potential stabilization criterion to calculate the preferred regioisomer. Experimental and calculated regioselectivity agree in the vast majority of cases. It was concluded that predominance of a single regioisomer can be obtained by maximizing (i) the chemical potential difference between nitrilimine and alkene and (ii) the local softness difference between the reactive atomic sites within each reactant. Such maximization can be achieved by carefully selecting the substituents on both reactants. Full article
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3224 KiB  
Article
A Computational Study of Structure and Reactivity of N-Substitued-4-Piperidones Curcumin Analogues and Their Radical Anions
by Maximiliano Martínez-Cifuentes, Boris Weiss-López and Ramiro Araya-Maturana
Molecules 2016, 21(12), 1658; https://doi.org/10.3390/molecules21121658 - 02 Dec 2016
Cited by 6 | Viewed by 5397
Abstract
In this work, a computational study of a series of N-substitued-4-piperidones curcumin analogues is presented. The molecular structure of the neutral molecules and their radical anions, as well as their reactivity, are investigated. N-substituents include methyl and benzyl groups, while substituents [...] Read more.
In this work, a computational study of a series of N-substitued-4-piperidones curcumin analogues is presented. The molecular structure of the neutral molecules and their radical anions, as well as their reactivity, are investigated. N-substituents include methyl and benzyl groups, while substituents on the aromatic rings cover electron-donor and electron-acceptor groups. Substitutions at the nitrogen atom do not significantly affect the geometry and frontier molecular orbitals (FMO) energies of these molecules. On the other hand, substituents on the aromatic rings modify the distribution of FMO. In addition, they influence the capability of these molecules to attach an additional electron, which was studied through adiabatic (AEA) and vertical electron affinities (VEA), as well as vertical detachment energy (VDE). To study electrophilic properties of these structures, local reactivity indices, such as Fukui (f+) and Parr (P+) functions, were calculated, and show the influence of the aromatic rings substituents on the reactivity of α,β-unsaturated ketones towards nucleophilic attack. This study has potential implications for the design of curcumin analogues based on a 4-piperidone core with desired reactivity. Full article
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377 KiB  
Article
A Molecular Electron Density Theory Study of the Chemical Reactivity of Cis- and Trans-Resveratrol
by Juan Frau, Francisco Muñoz and Daniel Glossman-Mitnik
Molecules 2016, 21(12), 1650; https://doi.org/10.3390/molecules21121650 - 01 Dec 2016
Cited by 33 | Viewed by 5199
Abstract
The chemical reactivity of resveratrol isomers with the potential to play a role as inhibitors of the nonenzymatic glycation of amino acids and proteins, both acting as antioxidants and as chelating agents for metallic ions such as Cu, Al and Fe, have been [...] Read more.
The chemical reactivity of resveratrol isomers with the potential to play a role as inhibitors of the nonenzymatic glycation of amino acids and proteins, both acting as antioxidants and as chelating agents for metallic ions such as Cu, Al and Fe, have been studied by resorting to the latest family of Minnesota density functionals. The chemical reactivity descriptors have been calculated through Molecular Electron Density Theory encompassing Conceptual DFT. The active sites for nucleophilic and electrophilic attacks have been chosen by relating them to the Fukui function indices, the dual descriptor f ( 2 ) ( r ) and the electrophilic and nucleophilic Parr functions. The validity of “Koopmans’ theorem in DFT” has been assessed by means of a comparison between the descriptors calculated through vertical energy values and those arising from the HOMO and LUMO values. Full article
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246 KiB  
Article
Statistical Significance of the Maximum Hardness Principle Applied to Some Selected Chemical Reactions
by Ranajit Saha, Sudip Pan and Pratim K. Chattaraj
Molecules 2016, 21(11), 1477; https://doi.org/10.3390/molecules21111477 - 05 Nov 2016
Cited by 7 | Viewed by 4705
Abstract
The validity of the maximum hardness principle (MHP) is tested in the cases of 50 chemical reactions, most of which are organic in nature and exhibit anomeric effect. To explore the effect of the level of theory on the validity of MHP in [...] Read more.
The validity of the maximum hardness principle (MHP) is tested in the cases of 50 chemical reactions, most of which are organic in nature and exhibit anomeric effect. To explore the effect of the level of theory on the validity of MHP in an exothermic reaction, B3LYP/6-311++G(2df,3pd) and LC-BLYP/6-311++G(2df,3pd) (def2-QZVP for iodine and mercury) levels are employed. Different approximations like the geometric mean of hardness and combined hardness are considered in case there are multiple reactants and/or products. It is observed that, based on the geometric mean of hardness, while 82% of the studied reactions obey the MHP at the B3LYP level, 84% of the reactions follow this rule at the LC-BLYP level. Most of the reactions possess the hardest species on the product side. A 50% null hypothesis is rejected at a 1% level of significance. Full article
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1257 KiB  
Article
A Theoretical Study of the Relationship between the Electrophilicity ω Index and Hammett Constant σp in [3+2] Cycloaddition Reactions of Aryl Azide/Alkyne Derivatives
by Hicham Ben El Ayouchia, Hafid Anane, Moulay Lahcen El Idrissi Moubtassim, Luis R. Domingo, Miguel Julve and Salah-Eddine Stiriba
Molecules 2016, 21(11), 1434; https://doi.org/10.3390/molecules21111434 - 27 Oct 2016
Cited by 8 | Viewed by 6029
Abstract
The relationship between the electrophilicity ω index and the Hammett constant σp has been studied for the [2+3] cycloaddition reactions of a series of para-substituted phenyl azides towards para-substituted phenyl alkynes. The electrophilicity ω index—a reactivity density functional theory (DFT) [...] Read more.
The relationship between the electrophilicity ω index and the Hammett constant σp has been studied for the [2+3] cycloaddition reactions of a series of para-substituted phenyl azides towards para-substituted phenyl alkynes. The electrophilicity ω index—a reactivity density functional theory (DFT) descriptor evaluated at the ground state of the molecules—shows a good linear relationship with the Hammett substituent constants σp. The theoretical scale of reactivity correctly explains the electrophilic activation/deactivation effects promoted by electron-withdrawing and electron-releasing substituents in both azide and alkyne components. Full article
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2097 KiB  
Article
Theoretical Study on Regioselectivity of the Diels-Alder Reaction between 1,8-Dichloroanthracene and Acrolein
by Mujeeb A. Sultan, Usama Karama, Abdulrahman I. Almansour and Saied M. Soliman
Molecules 2016, 21(10), 1277; https://doi.org/10.3390/molecules21101277 - 23 Sep 2016
Cited by 6 | Viewed by 5577
Abstract
A theoretical study of the regioselectivity of the Diels-Alder reaction between 1,8-dichloroanthracene and acrolein is performed using DFT at the B3LYP/6-31G(d,p) level of theory. The FMO analysis, global and local reactivity indices confirmed the reported experimental results. Potential energy surface analysis showed that [...] Read more.
A theoretical study of the regioselectivity of the Diels-Alder reaction between 1,8-dichloroanthracene and acrolein is performed using DFT at the B3LYP/6-31G(d,p) level of theory. The FMO analysis, global and local reactivity indices confirmed the reported experimental results. Potential energy surface analysis showed that the cycloadditions (CAs) favor the formation of the anti product. These results are in good agreement with the reported results obtained experimentally where the anti is the major product. Full article
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2874 KiB  
Article
X-ray Single Crystal Structure, DFT Calculations and Biological Activity of 2-(3-Methyl-5-(pyridin-2’-yl)-1H-pyrazol-1-yl) Ethanol
by Smaail Radi, Ahmed Attayibat, Mohamed El-Massaoudi, Amin Salhi, Driss Eddike, Monique Tillard and Yahia N. Mabkhot
Molecules 2016, 21(8), 1020; https://doi.org/10.3390/molecules21081020 - 05 Aug 2016
Cited by 7 | Viewed by 5057
Abstract
A pyridylpyrazole bearing a hydroxyethyl substituent group has been synthesized by condensation of (Z)-4-hydroxy-4-(pyridin-2-yl)but-3-en-2-one with 2-hydroxyethylhydrazine. The compound was well characterized and its structure confirmed by single crystal X-ray diffraction. Density functional calculations have been performed using DFT method with 6-31G* [...] Read more.
A pyridylpyrazole bearing a hydroxyethyl substituent group has been synthesized by condensation of (Z)-4-hydroxy-4-(pyridin-2-yl)but-3-en-2-one with 2-hydroxyethylhydrazine. The compound was well characterized and its structure confirmed by single crystal X-ray diffraction. Density functional calculations have been performed using DFT method with 6-31G* basis set. The HOMO-LUMO energy gap, binding energies and electron deformation densities are calculated at the DFT (BLYP, PW91, PWC) level. The electrophilic f(−) and nucleophilic f(+) Fukui functions and also the electrophilic and nucleophilic Parr functions are well adapted to find the electrophile and nucleophile centers in the molecule. The title compound has been tested for its DPPH radical scavenging activity which is involved in aging processes, anti-inflammatory, anticancer and wound healing activity. Compound is also found with a significant antioxidant activity, probably due to the ability to donate a hydrogen atom to the DPPH radical. Full article
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Review

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3597 KiB  
Review
Applications of the Conceptual Density Functional Theory Indices to Organic Chemistry Reactivity
by Luis R. Domingo, Mar Ríos-Gutiérrez and Patricia Pérez
Molecules 2016, 21(6), 748; https://doi.org/10.3390/molecules21060748 - 09 Jun 2016
Cited by 794 | Viewed by 17194
Abstract
Theoretical reactivity indices based on the conceptual Density Functional Theory (DFT) have become a powerful tool for the semiquantitative study of organic reactivity. A large number of reactivity indices have been proposed in the literature. Herein, global quantities like the electronic chemical potential [...] Read more.
Theoretical reactivity indices based on the conceptual Density Functional Theory (DFT) have become a powerful tool for the semiquantitative study of organic reactivity. A large number of reactivity indices have been proposed in the literature. Herein, global quantities like the electronic chemical potential μ, the electrophilicity ω and the nucleophilicity N indices, and local condensed indices like the electrophilic P k + and nucleophilic P k Parr functions, as the most relevant indices for the study of organic reactivity, are discussed. Full article
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