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Quantum Chemical Calculations of Molecular Reaction Processes
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Quantum Chemical Calculations of Molecular Reaction Processes

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

Deadline for manuscript submissions: 30 April 2025 | Viewed by 1073

Special Issue Editors

Dr. Naoki Kishimoto

E-Mail Website
Guest Editor
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3, Aoba, Aramaki, Aoba-ku, Sendai 980-8578, Japan
Interests: quantum chemical calculation; theory of chemical reaction; molecular dynamics calculation; spectroscopy; intermolecular interaction; polymer; nano chemistry; supramolecule; composite material
Prof. Dr. Shiro Koseki

E-Mail Website
Guest Editor
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3, Aoba, Aramaki, Aoba-ku, Sendai 980-8578, Japan
Interests: computational chemistry; quantum chemical calculations

Special Issue Information

Dear Colleagues,

Theoretical chemical calculations are becoming increasingly important in molecular science and are indispensable for elucidating complex chemical reaction processes and quantitatively predicting observations. The accuracy of quantum chemical calculations has been supported by developments in electronic state theory and the increasing speed of computers. In quantum chemical calculations for reactions, novel algorithms have been developed to reveal reaction pathways, and eventually artificial intelligence will be used to a great extent for molecular design.

In this Special Issue, we feature papers that use quantum chemical calculations to reveal the reaction processes of molecules. We then publish the latest results on using computers to understand the complex world of chemistry as an open access journal, making the potential of quantum chemical calculations widely known to the world.

Dr. Naoki Kishimoto
Prof. Dr. Shiro Koseki
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 submissions that pass pre-check are 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 semimonthly 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 2700 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.

Keywords

  • computational chemistry
  • electronic structure
  • MO theory
  • DFT calculation
  • potential energy surface
  • reaction process
  • ab initio molecular dynamics
  • molecular design

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Further information on MDPI's Special Issue policies can be found here.

Published Papers (2 papers)

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Research

Jump to: Review

18 pages, 5267 KiB  
Article
The Puzzle of the Regioselectivity and Molecular Mechanism of the (3+2) Cycloaddition Reaction Between E-2-(Trimethylsilyl)-1-Nitroethene and Arylonitrile N-Oxides: Molecular Electron Density Theory (MEDT) Quantumchemical Study
by Mikołaj Sadowski, Ewa Dresler and Radomir Jasiński
Molecules 2025, 30(4), 974; https://doi.org/10.3390/molecules30040974 - 19 Feb 2025
Viewed by 243
Abstract
The regioselectivity and molecular mechanism of the (3+2) cycloaddition reaction between E-2-(trimethylsilyl)-1-nitroethene and arylonitrile N-oxides were explored on the basis of the ωB97XD/6-311+G(d) (PCM) quantumchemical calculations. It was found that the earlier postulate regarding the regioselectivity of the cycloaddition stage should [...] Read more.
The regioselectivity and molecular mechanism of the (3+2) cycloaddition reaction between E-2-(trimethylsilyl)-1-nitroethene and arylonitrile N-oxides were explored on the basis of the ωB97XD/6-311+G(d) (PCM) quantumchemical calculations. It was found that the earlier postulate regarding the regioselectivity of the cycloaddition stage should be undermined. Within our research, several aspects of the title reaction were also examined: interactions between reagents, electronic structures of alkenes and nitrile oxides, the nature of transition states, the influence of the polarity solvent on the reaction selectivity and mechanism, substituent effects, etc. The obtained results offer a general conclusion for all of the important aspects of some groups of cycloaddition processes. Full article
(This article belongs to the Special Issue Quantum Chemical Calculations of Molecular Reaction Processes)
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Figure 1

Figure 1
<p>To the left: topology of the ELF function. Monosynaptic valence basins given in red, disynaptic in green, protonated basins in cyan, and core basins in magenta. To the right: positions of ELF attractors (in magenta) and populations of significant basins (isovalue = 0.75). Results for compounds <b>1</b> and <b>6</b> as computed via <span class="html-italic">ω</span>B97XD/6-311G(d).</p> Full article ">Figure 2
<p>Natural charges of atoms (in electrons) in compounds <b>1</b> and <b>6</b> as computed at the ground state in gaseous phase (<span class="html-italic">ω</span>B97XD/6-311G(d)); charges &gt; 0.2 e are given in red, charges &lt; −0.2 are given in blue, and other charges are given in black. Methyl groups within XMe<sub>3</sub> (X = Si,C) substituents are equivalent; thus, only one is described in detail.</p> Full article ">Figure 3
<p>To the left: topology of the ELF function. Monosynaptic valence basins given in red, disynaptic in green, protonated basins in cyan, and core basins in magenta. To the right: positions of ELF attractors (in magenta) and populations of significant basins (isovalue = 0.75). Results for <span class="html-italic">N</span>-oxides <b>2a</b>–<b>c</b> as computed via <span class="html-italic">ω</span>B97XD/6-311G(d).</p> Full article ">Figure 4
<p>Natural charges of atoms (in electrons) in compounds <b>2a</b>–<b>c</b> as computed at the ground state in gaseous phase (<span class="html-italic">ω</span>B97XD/6-311G(d)); charges &gt; 0.2 e are given in red, charges &lt; −0.2 are given in blue, and other charges are given in black.</p> Full article ">Figure 5
<p>Views of critical structures for the (3+2) cycloaddition reaction between E-2-(trimethylsilyl)-1-nitroethene (<b>1</b>) and benzonitrile <span class="html-italic">N</span>-oxide (<b>2a</b>) in the CCl<sub>4</sub> solution in light of the <span class="html-italic">ω</span>B97XD/6-311+G(d) (PCM) calculations.</p> Full article ">Figure 6
<p>To the left: topology of the ELF function. Monosynaptic valence basins given in red, disynaptic in green, protonated basins in cyan, and core basins in magenta (isovalue = 0.75). The blue dashed lines signify which atoms will bond if the TS transforms to the products. To the right: positions of ELF attractors (<span class="html-italic">ω</span>B97XD/6-311G(d) PCM-CCl<sub>4</sub>.</p> Full article ">Figure 7
<p>Natural charges of atoms (in electrons) in <b>TSA</b> and <b>TSB</b> as computed at the ground state in gaseous phase (<span class="html-italic">ω</span>B97XD/6-311G(d), PCM CCl<sub>4</sub>); charges &gt; 0.2 e are given in red, charges &lt; −0.2 are given in blue, and other charges are given in black.</p> Full article ">Scheme 1
<p>Experimentally observed course of the (3+2) cycloaddition reaction between E-2-(trimethylsilyl)-1-nitroethene (<b>1</b>) and benzonitrile <span class="html-italic">N</span>-oxide (<b>2a</b>).</p> Full article ">Scheme 2
<p>Experimentally observed course of the (3+2) cycloaddition reaction between E-3,3,3-trichloro-1-nitroprop-1-ene and arylonitrile <span class="html-italic">N</span>-oxides.</p> Full article ">Scheme 3
<p>The stepwise zwitterionic mechanism of the 32CA between trifluroacetonitrile <span class="html-italic">N</span>-oxide and vinylamine.</p> Full article ">Scheme 4
<p>The stepwise biradical mechanism of the 32CA between acetonitrile <span class="html-italic">N</span>-oxide and tetraaminoethene.</p> Full article ">Scheme 5
<p>The formation of the zwitterionic intermediate in the reaction between nitroacetylene and arylonitrile <span class="html-italic">N</span>-oxides.</p> Full article ">Scheme 6
<p>Theoretical possibility of the regioisomeric paths of the (3+2) cycloaddition reaction between E-2-(trimethylsilyl)-1-nitroethene (<b>1</b>) and benzonitrile <span class="html-italic">N</span>-oxide (<b>2a</b>).</p> Full article ">Scheme 7
<p>Resonance structures proposed by Rattananakin et al. for 2-amino-1-nitroethene [<a href="#B41-molecules-30-00974" class="html-bibr">41</a>].</p> Full article ">Scheme 8
<p>Experimentally observed course of the (3+2) cycloaddition reaction between 1-(trimethylsilyl)-1-acetylethene (<b>7</b>) and benzonitrile <span class="html-italic">N</span>-oxide (<b>2a</b>).</p> Full article ">

Review

Jump to: Research

25 pages, 3152 KiB  
Review
Thermal and Photochemical Reactions of Organosilicon Compounds
by Masae Takahashi
Molecules 2025, 30(5), 1158; https://doi.org/10.3390/molecules30051158 - 4 Mar 2025
Viewed by 161
Abstract
This article provides a comprehensive review of quantum chemical computational studies on the thermal and photochemical reactions of organosilicon compounds, based on fundamental concepts such as initial complex formation, HOMO-LUMO interactions, and subjacent orbital interactions. Despite silicon’s position in group 14 of the [...] Read more.
This article provides a comprehensive review of quantum chemical computational studies on the thermal and photochemical reactions of organosilicon compounds, based on fundamental concepts such as initial complex formation, HOMO-LUMO interactions, and subjacent orbital interactions. Despite silicon’s position in group 14 of the periodic table, alongside carbon, its reactivity patterns exhibit significant deviations from those of carbon. This review delves into the reactivity behaviors of organosilicon compounds, particularly focusing on the highly coordinated nature of silicon. It is poised to serve as a valuable resource for chemists, offering insights into cutting-edge research and fostering further innovations in synthetic chemistry and also theoretical chemistry. Full article
(This article belongs to the Special Issue Quantum Chemical Calculations of Molecular Reaction Processes)
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Figure 1

Figure 1
<p>1,2-Addition reaction of molecule XY to doubly bonded compound RHM1=M2H<sub>2</sub>, resulting in two regioselective products RHXM1–M2YH<sub>2</sub> and RHYM1–M2XH<sub>2</sub> via pathways 1 and 2, respectively. For water addition to disilene, X, Y, M1, and M2 are H, OH, Si, and Si, respectively.</p> Full article ">Figure 2
<p>HOMO–LUMO interaction between molecule XY and doubly bonded compound RHM1=M2H<sub>2</sub>.</p> Full article ">Figure 3
<p>Energy diagram for the water-addition reaction to disilene. C<sub>L</sub>, TS<sub>L</sub>, and P<sub>A</sub> are the same as C’<sub>L</sub>, TS’<sub>L</sub>, and P<sub>S</sub>, respectively, in the water-addition reaction to disilene, as the two silicon atoms in disilene are not distinguished.</p> Full article ">Figure 4
<p>Generalized mechanism for nucleophilic addition of ammonia to disilene.</p> Full article ">Figure 5
<p>1,3-Silyl migration of allylsilanes with symmetry-allowed suprafacial inversion of configuration at the migrating silicon.</p> Full article ">Figure 6
<p>The trigonal bipyramidal (TBP) and square pyramidal (SP) transition structures in 1,3-sigmatropic silyl migration of allylsilanes.</p> Full article ">Figure 7
<p>Interaction diagram of frontier orbitals in TBP and SP transition structures for 1,3-silyl migration of allylsilanes. The frontier orbitals of the silyl and allyl radicals interacting in the transition structures are constructed by the three π orbitals (<span class="html-italic">ϕ</span><sub>1</sub>, <span class="html-italic">ϕ</span><sub>2</sub>, and <span class="html-italic">ϕ</span><sub>3</sub>) of the allyl radical and the three 3p orbitals (<span class="html-italic">θ</span><sub>1</sub>, <span class="html-italic">θ</span><sub>2</sub>, and <span class="html-italic">θ</span><sub>3</sub>) or (<span class="html-italic">θ</span>’<sub>1</sub>, <span class="html-italic">θ</span>’<sub>2</sub>, and <span class="html-italic">θ</span>’<sub>3</sub>) of the silyl radical. The symmetry notations S (symmetric) and A (antisymmetric) refer to the planes that bisect the ally CCC plane.</p> Full article ">Figure 8
<p>Photochemical reactions of cyclopropenylidene (<b>1</b>) and silacyclopropenylidene (<b>3</b>).</p> Full article ">Figure 9
<p>A characteristic conical intersection (CI) structure common to photochemical sigmatropic shifts reported as a ubiquitous control element [<a href="#B194-molecules-30-01158" class="html-bibr">194</a>].</p> Full article ">
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