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Special Issue "The Molecular Electron Density Theory: A Modern View of Molecular Reactivity in Organic Chemistry"

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

Deadline for manuscript submissions: 30 December 2017

Special Issue Editors

Guest Editor
Prof. Dr. Luis R. Domingo, FRSC

Department of Organic Chemistry, University of Valencia, Dr. Moliner 50, 46100 Burjassot, Valencia, Spain
Website | E-Mail
Interests: theoretical organic chemistry; molecular electron density theory; density functional theory; conceptual DFT reactivity indices; electron localisation function; bonding evolution theory; non-covalent Interactions; molecular mechanisms; reactivity; selectivity
Guest Editor
Prof. Dr. Miquel Solà

Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, c/ Maria Aurèlia Capmany 6, 17003 Girona, Catalonia, Spain
Website | E-Mail
Interests: computational and theoretical chemistry; density functional theory; conceptual DFT reactivity indices; electron delocalisation; conjugation; aromaticity; molecular clusters; molecular mechanisms; reactivity

Special Issue Information

Dear Colleagues,

Recently, the Molecular Electron Density Theory (MEDT), in which changes in electron density along an organic reaction, and not molecular orbital (MO) interactions, are responsible for the molecular organic reactivity, has been proposed (Molecules 2016, 21, 1319).

Since 1965, the Frontier Molecular Orbital (FMO) theory has been widely used in Organic Chemistry as a theoretical model to study chemical reactivity. However, such as with Schrödinger’s wavefunction, MOs have no physical significance; only the square of the wavefunction is related to the electron density, which is the only physically-observable factor.

Parallel to the establishment of the FMO theory, the Conceptual Density Functional Theory (CDFT), a DFT-subfield that allows the study the molecular reactivity at the ground state, was developed. Later, the Quantum Theory of Atoms in Molecules (QTAIM) and the Electron Localisation Function (ELF), which permit the topological analysis of the molecular electron density, were developed. Finally, Non-Covalent Interaction (NCIs) analyses have been recently proposed for the study of weak interactions.

All these quantum chemical tools, which allow the analysis of the molecular electron density, let know the electronic structure of the species involved in an organic reaction, and thus, to study chemical organic reactivity from a modern point of view based on electron density being the only physical observable.

The present Special Issue will collect theoretical studies based on the MEDT, with the aim of establishing and spreading a new perspective of the chemical organic reactivity based only on the analysis of the molecular electron density.

Keywords

  • Molecular Electron Density Theory
  • Electron Density
  • Chemical Organic Reactivity
  • Reaction Mechanisms
  • Conceptual Density Functional Theory Indices
  • Electron Localisation Function
  • Quantum Theory of Atoms in Molecules
  • Bonding Evolution Theory
  • Non Covalent interactions

Prof. Dr. Luis R. Domingo
Prof. Dr. Miquel Solà
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1800 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Published Papers (4 papers)

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Research

Open AccessArticle Mechanistic Study of Copper-Catalyzed C-H Hydroxylation/C-S Coupling by ESI-HR MS and DFT Calculations
Molecules 2017, 22(11), 1912; doi:10.3390/molecules22111912
Received: 6 October 2017 / Accepted: 1 November 2017 / Published: 6 November 2017
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Abstract
The reaction mechanism of Cu-catalyzed C-H hydroxylation/C-S coupling was studied using electrospray ionization high resolution mass spectrometry (ESI-HR MS) and density functional theory calculations (DFT). Notably, a series of CuI and CuIII complexes were observed as key intermediates and identified using
[...] Read more.
The reaction mechanism of Cu-catalyzed C-H hydroxylation/C-S coupling was studied using electrospray ionization high resolution mass spectrometry (ESI-HR MS) and density functional theory calculations (DFT). Notably, a series of CuI and CuIII complexes were observed as key intermediates and identified using ESI-HR MS. Furthermore, a catalyst cycle involving proton abstraction/oxidative addition/reductive elimination was proposed. This study is important and valuable with respect to C-H functionalization. Full article
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Open AccessFeature PaperArticle BET & ELF Quantum Topological Analysis of Neutral 2-Aza-Cope Rearrangement of γ-Alkenyl Nitrones
Molecules 2017, 22(8), 1371; doi:10.3390/molecules22081371
Received: 6 August 2017 / Revised: 15 August 2017 / Accepted: 18 August 2017 / Published: 19 August 2017
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Abstract
The 2-Aza-Cope rearrangement of γ-alkenyl nitrones is a rare example of the neutral thermal 2-aza-Cope process that usually takes place with cationic species. During the rearrangement, a redistribution of bonds and electronic density occurs in one kinetic step. However, the introduction of substituents
[...] Read more.
The 2-Aza-Cope rearrangement of γ-alkenyl nitrones is a rare example of the neutral thermal 2-aza-Cope process that usually takes place with cationic species. During the rearrangement, a redistribution of bonds and electronic density occurs in one kinetic step. However, the introduction of substituents with different steric requirements and electronic features might alter the activation energies and the synchronicity of the reaction. The electron localization function (ELF) analysis and its application to Bonding Evolution Theory (BET) analysis within the context of Molecular Electron Density Theory (MEDT) is an excellent tool to monitor the electron density along the reaction coordinate and thus investigate in detail bond breaking and formation and the corresponding energy barriers. By analyzing topological ELF calculations of seventeen 2-aza-Cope nitrone rearrangements with selected substituents, the main factors influencing the synchronicity of the process were investigated. This MEDT study results revealed that the rearrangement is a non-polar process mostly influenced by steric factors rather than by electronic ones, and confirms the pseudoradical character of the process rather than any pericyclic electron-reorganization. Full article
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Open AccessArticle A Molecular Electron Density Theory Study of the Reactivity of Azomethine Imine in [3+2] Cycloaddition Reactions
Molecules 2017, 22(5), 750; doi:10.3390/molecules22050750
Received: 10 April 2017 / Revised: 28 April 2017 / Accepted: 30 April 2017 / Published: 6 May 2017
Cited by 3 | PDF Full-text (5112 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The electronic structure and the participation of the simplest azomethine imine (AI) in [3+2] cycloaddition (32CA) reactions have been analysed within the Molecular Electron Density Theory (MEDT) using Density Functional Theory (DFT) calculations at the MPWB1K/6-311G(d) level. Topological analysis of the electron localisation
[...] Read more.
The electronic structure and the participation of the simplest azomethine imine (AI) in [3+2] cycloaddition (32CA) reactions have been analysed within the Molecular Electron Density Theory (MEDT) using Density Functional Theory (DFT) calculations at the MPWB1K/6-311G(d) level. Topological analysis of the electron localisation function reveals that AI has a pseudoradical structure, while the conceptual DFT reactivity indices characterises this three-atom-component (TAC) as a moderate electrophile and a good nucleophile. The non-polar 32CA reaction of AI with ethylene takes place through a one-step mechanism with moderate activation energy, 8.7 kcal·mol−1. A bonding evolution theory study indicates that this reaction takes place through a non-concerted [2n + 2τ] mechanism in which the C–C bond formation is clearly anticipated prior to the C–N one. On the other hand, the polar 32CA reaction of AI with dicyanoethylene takes place through a two-stage one-step mechanism. Now, the activation energy is only 0.4 kcal·mol−1, in complete agreement with the high polar character of the more favourable regioisomeric transition state structure. The current MEDT study makes it possible to extend Domingo’s classification of 32CA reactions to a new pseudo(mono)radical type (pmr-type) of reactivity. Full article
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Open AccessArticle Computational Prediction of the Protonation Sites of Ac-Lys-(Ala)n-Lys-NH2 Peptides through Conceptual DFT Descriptors
Molecules 2017, 22(3), 458; doi:10.3390/molecules22030458
Received: 6 February 2017 / Accepted: 10 March 2017 / Published: 13 March 2017
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Abstract
Six density functionals (M11, M11L, MN12L, MN12SX, N12, and N12SX) in connection with the Def2TZVP basis set and the SMD solvation model (water as a solvent) have been assessed for the calculation of the molecular structure and properties of several peptides with the
[...] Read more.
Six density functionals (M11, M11L, MN12L, MN12SX, N12, and N12SX) in connection with the Def2TZVP basis set and the SMD solvation model (water as a solvent) have been assessed for the calculation of the molecular structure and properties of several peptides with the general formulaAc-Lys-(Ala)n-Lys-NH2,withn=0to5  [...] Full article
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