Insights into the Factors Controlling the Origin of Activation Barriers in the [2 + 2] Cycloaddition Reactions of Heavy Imine-like Molecules Featuring a Ge=Group 15 Double Bond with Heterocumulenes
The [2 + 2] cycloaddition reactions of the heterocumulene (<b>N=C=N</b>) with the heavy imine-like molecule <b>Ge=G15-Rea</b> (G15 = Group 15 element) were examined using density functional theory (M06-2X-D3/def2-TZVP). The theoretical findings indicate that the doubly bonded...
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2025-04-01
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| author | Zheng-Feng Zhang Ming-Der Su |
| author_facet | Zheng-Feng Zhang Ming-Der Su |
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| description | The [2 + 2] cycloaddition reactions of the heterocumulene (<b>N=C=N</b>) with the heavy imine-like molecule <b>Ge=G15-Rea</b> (G15 = Group 15 element) were examined using density functional theory (M06-2X-D3/def2-TZVP). The theoretical findings indicate that the doubly bonded Ge=G15 moiety in <b>Ge=G15-Rea</b> (L<sub>1</sub>L<sub>2</sub>Ge=G15L<sub>3</sub>) is characterized by electron-sharing bonding between the triplet L<sub>1</sub>L<sub>2</sub>Ge and triplet G15–L<sub>3</sub> fragments. All five Ge=G15-based heavy imine analogues readily undergo [2 + 2] cycloaddition reactions with <b>N=C=N</b>. Energy decomposition analysis (EDA–NOCV) suggests that the [2 + 2] cycloaddition reaction between <b>Ge=G15-Rea</b> and <b>N=C=N</b> involves a donor–acceptor (singlet–singlet) interaction instead of an electron-sharing (triplet–triplet) interaction. Frontier molecular orbital (FMO) theory and the energy decomposition analysis–natural orbitals for chemical valence (EDA–NOCV) findings emphasize that the key bonding interaction involves the occupied p-π orbital of <b>Ge=G15-Rea</b> and the vacant p-π* orbital of <b>C=N=C</b>. Based on the activation strain model results, the activation barrier of the [2 + 2] cycloaddition reaction is predominantly controlled by the deformation energies of <b>Ge=G15-Rea</b> and <b>N=C=N</b>. |
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| spelling | doaj-art-8fa3016e72db49cf998922b58374de832025-08-20T02:59:14ZengMDPI AGMolecules1420-30492025-04-01309190510.3390/molecules30091905Insights into the Factors Controlling the Origin of Activation Barriers in the [2 + 2] Cycloaddition Reactions of Heavy Imine-like Molecules Featuring a Ge=Group 15 Double Bond with HeterocumulenesZheng-Feng Zhang0Ming-Der Su1Department of Applied Chemistry, National Chiayi University, Chiayi 60004, TaiwanDepartment of Applied Chemistry, National Chiayi University, Chiayi 60004, TaiwanThe [2 + 2] cycloaddition reactions of the heterocumulene (<b>N=C=N</b>) with the heavy imine-like molecule <b>Ge=G15-Rea</b> (G15 = Group 15 element) were examined using density functional theory (M06-2X-D3/def2-TZVP). The theoretical findings indicate that the doubly bonded Ge=G15 moiety in <b>Ge=G15-Rea</b> (L<sub>1</sub>L<sub>2</sub>Ge=G15L<sub>3</sub>) is characterized by electron-sharing bonding between the triplet L<sub>1</sub>L<sub>2</sub>Ge and triplet G15–L<sub>3</sub> fragments. All five Ge=G15-based heavy imine analogues readily undergo [2 + 2] cycloaddition reactions with <b>N=C=N</b>. Energy decomposition analysis (EDA–NOCV) suggests that the [2 + 2] cycloaddition reaction between <b>Ge=G15-Rea</b> and <b>N=C=N</b> involves a donor–acceptor (singlet–singlet) interaction instead of an electron-sharing (triplet–triplet) interaction. Frontier molecular orbital (FMO) theory and the energy decomposition analysis–natural orbitals for chemical valence (EDA–NOCV) findings emphasize that the key bonding interaction involves the occupied p-π orbital of <b>Ge=G15-Rea</b> and the vacant p-π* orbital of <b>C=N=C</b>. Based on the activation strain model results, the activation barrier of the [2 + 2] cycloaddition reaction is predominantly controlled by the deformation energies of <b>Ge=G15-Rea</b> and <b>N=C=N</b>.https://www.mdpi.com/1420-3049/30/9/1905[2 + 2] cycloadditionheterocumuleneheavy iminedonor–acceptor interactionelectron-sharing |
| spellingShingle | Zheng-Feng Zhang Ming-Der Su Insights into the Factors Controlling the Origin of Activation Barriers in the [2 + 2] Cycloaddition Reactions of Heavy Imine-like Molecules Featuring a Ge=Group 15 Double Bond with Heterocumulenes Molecules [2 + 2] cycloaddition heterocumulene heavy imine donor–acceptor interaction electron-sharing |
| title | Insights into the Factors Controlling the Origin of Activation Barriers in the [2 + 2] Cycloaddition Reactions of Heavy Imine-like Molecules Featuring a Ge=Group 15 Double Bond with Heterocumulenes |
| title_full | Insights into the Factors Controlling the Origin of Activation Barriers in the [2 + 2] Cycloaddition Reactions of Heavy Imine-like Molecules Featuring a Ge=Group 15 Double Bond with Heterocumulenes |
| title_fullStr | Insights into the Factors Controlling the Origin of Activation Barriers in the [2 + 2] Cycloaddition Reactions of Heavy Imine-like Molecules Featuring a Ge=Group 15 Double Bond with Heterocumulenes |
| title_full_unstemmed | Insights into the Factors Controlling the Origin of Activation Barriers in the [2 + 2] Cycloaddition Reactions of Heavy Imine-like Molecules Featuring a Ge=Group 15 Double Bond with Heterocumulenes |
| title_short | Insights into the Factors Controlling the Origin of Activation Barriers in the [2 + 2] Cycloaddition Reactions of Heavy Imine-like Molecules Featuring a Ge=Group 15 Double Bond with Heterocumulenes |
| title_sort | insights into the factors controlling the origin of activation barriers in the 2 2 cycloaddition reactions of heavy imine like molecules featuring a ge group 15 double bond with heterocumulenes |
| topic | [2 + 2] cycloaddition heterocumulene heavy imine donor–acceptor interaction electron-sharing |
| url | https://www.mdpi.com/1420-3049/30/9/1905 |
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