Five Bonds to Carbon through Tri-Coordination in <inline-formula><math display="inline"><semantics><mrow><msub><mrow><mi>Al</mi></mrow><mn>3</mn></msub><msubsup><mi mathvariant="normal">C</mi><mn>3</mn><mrow><mo>−</mo><mo>/</mo><mn>0</mn></mrow></msubsup></mrow></semantics></math></inline-formula>
Here, five bonds to carbon through tri-coordination are theoretically established in the global minimum energy isomers of <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow><mi>A...
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MDPI AG
2023-05-01
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| author | Abdul Hamid Malhan Venkatesan S. Thimmakondu Krishnan Thirumoorthy |
| author_facet | Abdul Hamid Malhan Venkatesan S. Thimmakondu Krishnan Thirumoorthy |
| author_sort | Abdul Hamid Malhan |
| collection | DOAJ |
| description | Here, five bonds to carbon through tri-coordination are theoretically established in the global minimum energy isomers of <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow><mi>Al</mi></mrow><mn>3</mn></msub><msubsup><mi mathvariant="normal">C</mi><mn>3</mn><mo>−</mo></msubsup></mrow></semantics></math></inline-formula> anion (<b>1a</b>) and <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow><mi>Al</mi></mrow><mn>3</mn></msub><msub><mi mathvariant="normal">C</mi><mn>3</mn></msub></mrow></semantics></math></inline-formula> neutral (<b>1n</b>) for the first time. Various isomers of <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow><mi>Al</mi></mrow><mn>3</mn></msub><msubsup><mi mathvariant="normal">C</mi><mn>3</mn><mrow><mo>−</mo><mo>/</mo><mn>0</mn></mrow></msubsup></mrow></semantics></math></inline-formula> are theoretically identified using density functional theory at the PBE0-D3/def2-TZVP level. Chemical bonding features are thoroughly analyzed for these two isomers (<b>1a</b> and <b>1n</b>) with different bonding and topological quantum chemical tools, such as adaptive natural density partitioning (AdNDP), Wiberg Bond Indices (WBIs), nucleus-independent chemical shifts (NICS), and atoms in molecules (AIM) analyses. The structure of isomer <b>1a</b> is planar with <i>C<sub>2v</sub></i> symmetry, whereas its neutral counterpart <b>1n</b> is non-planar with <i>C<sub>2</sub></i> symmetry, in which its terminal aluminum atoms are out of the plane. The central allenic carbon atom of isomers <b>1a</b> and <b>1n</b> exhibits tri-coordination and thus makes it a case of five bonds to carbon, which is confirmed through their total bond order as observed in WBI. Both the isomers show σ- and π-aromaticity and are predicted with the NICS and AdNDP analyses. Further, the results of ab initio molecular dynamics simulations reveal their kinetic stability at room temperature; thus, they are experimentally viable systems. |
| first_indexed | 2024-03-11T02:38:59Z |
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| spelling | doaj.art-9206a5a278be4c8da51afa0fc342ce802023-11-18T09:45:33ZengMDPI AGChemistry2624-85492023-05-01521113112310.3390/chemistry5020076Five Bonds to Carbon through Tri-Coordination in <inline-formula><math display="inline"><semantics><mrow><msub><mrow><mi>Al</mi></mrow><mn>3</mn></msub><msubsup><mi mathvariant="normal">C</mi><mn>3</mn><mrow><mo>−</mo><mo>/</mo><mn>0</mn></mrow></msubsup></mrow></semantics></math></inline-formula>Abdul Hamid Malhan0Venkatesan S. Thimmakondu1Krishnan Thirumoorthy2Department of Chemistry, School of Advanced Sciences, Vellore Institute of Technology, Vellore 632 014, Tamil Nadu, IndiaDepartment of Chemistry and Biochemistry, San Diego State University, San Diego, CA 92182-1030, USADepartment of Chemistry, School of Advanced Sciences, Vellore Institute of Technology, Vellore 632 014, Tamil Nadu, IndiaHere, five bonds to carbon through tri-coordination are theoretically established in the global minimum energy isomers of <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow><mi>Al</mi></mrow><mn>3</mn></msub><msubsup><mi mathvariant="normal">C</mi><mn>3</mn><mo>−</mo></msubsup></mrow></semantics></math></inline-formula> anion (<b>1a</b>) and <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow><mi>Al</mi></mrow><mn>3</mn></msub><msub><mi mathvariant="normal">C</mi><mn>3</mn></msub></mrow></semantics></math></inline-formula> neutral (<b>1n</b>) for the first time. Various isomers of <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow><mi>Al</mi></mrow><mn>3</mn></msub><msubsup><mi mathvariant="normal">C</mi><mn>3</mn><mrow><mo>−</mo><mo>/</mo><mn>0</mn></mrow></msubsup></mrow></semantics></math></inline-formula> are theoretically identified using density functional theory at the PBE0-D3/def2-TZVP level. Chemical bonding features are thoroughly analyzed for these two isomers (<b>1a</b> and <b>1n</b>) with different bonding and topological quantum chemical tools, such as adaptive natural density partitioning (AdNDP), Wiberg Bond Indices (WBIs), nucleus-independent chemical shifts (NICS), and atoms in molecules (AIM) analyses. The structure of isomer <b>1a</b> is planar with <i>C<sub>2v</sub></i> symmetry, whereas its neutral counterpart <b>1n</b> is non-planar with <i>C<sub>2</sub></i> symmetry, in which its terminal aluminum atoms are out of the plane. The central allenic carbon atom of isomers <b>1a</b> and <b>1n</b> exhibits tri-coordination and thus makes it a case of five bonds to carbon, which is confirmed through their total bond order as observed in WBI. Both the isomers show σ- and π-aromaticity and are predicted with the NICS and AdNDP analyses. Further, the results of ab initio molecular dynamics simulations reveal their kinetic stability at room temperature; thus, they are experimentally viable systems.https://www.mdpi.com/2624-8549/5/2/76<named-content content-type="inline-formula"><inline-formula><mml:math id="mm5"><mml:semantics><mml:mrow><mml:msub><mml:mrow><mml:mi>Al</mml:mi></mml:mrow><mml:mn>3</mml:mn></mml:msub><mml:msubsup><mml:mi mathvariant="normal">C</mml:mi><mml:mn>3</mml:mn><mml:mrow><mml:mo>−</mml:mo><mml:mo>/</mml:mo><mml:mn>0</mml:mn></mml:mrow></mml:msubsup></mml:mrow></mml:semantics></mml:math></inline-formula></named-content>five bonds to carbonanti-van’t Hoff-Le Belσ-aromaticityπ-aromaticitybonding |
| spellingShingle | Abdul Hamid Malhan Venkatesan S. Thimmakondu Krishnan Thirumoorthy Five Bonds to Carbon through Tri-Coordination in <inline-formula><math display="inline"><semantics><mrow><msub><mrow><mi>Al</mi></mrow><mn>3</mn></msub><msubsup><mi mathvariant="normal">C</mi><mn>3</mn><mrow><mo>−</mo><mo>/</mo><mn>0</mn></mrow></msubsup></mrow></semantics></math></inline-formula> Chemistry <named-content content-type="inline-formula"><inline-formula><mml:math id="mm5"><mml:semantics><mml:mrow><mml:msub><mml:mrow><mml:mi>Al</mml:mi></mml:mrow><mml:mn>3</mml:mn></mml:msub><mml:msubsup><mml:mi mathvariant="normal">C</mml:mi><mml:mn>3</mml:mn><mml:mrow><mml:mo>−</mml:mo><mml:mo>/</mml:mo><mml:mn>0</mml:mn></mml:mrow></mml:msubsup></mml:mrow></mml:semantics></mml:math></inline-formula></named-content> five bonds to carbon anti-van’t Hoff-Le Bel σ-aromaticity π-aromaticity bonding |
| title | Five Bonds to Carbon through Tri-Coordination in
<inline-formula><math display="inline"><semantics><mrow><msub><mrow><mi>Al</mi></mrow><mn>3</mn></msub><msubsup><mi mathvariant="normal">C</mi><mn>3</mn><mrow><mo>−</mo><mo>/</mo><mn>0</mn></mrow></msubsup></mrow></semantics></math></inline-formula> |
| title_full | Five Bonds to Carbon through Tri-Coordination in
<inline-formula><math display="inline"><semantics><mrow><msub><mrow><mi>Al</mi></mrow><mn>3</mn></msub><msubsup><mi mathvariant="normal">C</mi><mn>3</mn><mrow><mo>−</mo><mo>/</mo><mn>0</mn></mrow></msubsup></mrow></semantics></math></inline-formula> |
| title_fullStr | Five Bonds to Carbon through Tri-Coordination in
<inline-formula><math display="inline"><semantics><mrow><msub><mrow><mi>Al</mi></mrow><mn>3</mn></msub><msubsup><mi mathvariant="normal">C</mi><mn>3</mn><mrow><mo>−</mo><mo>/</mo><mn>0</mn></mrow></msubsup></mrow></semantics></math></inline-formula> |
| title_full_unstemmed | Five Bonds to Carbon through Tri-Coordination in
<inline-formula><math display="inline"><semantics><mrow><msub><mrow><mi>Al</mi></mrow><mn>3</mn></msub><msubsup><mi mathvariant="normal">C</mi><mn>3</mn><mrow><mo>−</mo><mo>/</mo><mn>0</mn></mrow></msubsup></mrow></semantics></math></inline-formula> |
| title_short | Five Bonds to Carbon through Tri-Coordination in
<inline-formula><math display="inline"><semantics><mrow><msub><mrow><mi>Al</mi></mrow><mn>3</mn></msub><msubsup><mi mathvariant="normal">C</mi><mn>3</mn><mrow><mo>−</mo><mo>/</mo><mn>0</mn></mrow></msubsup></mrow></semantics></math></inline-formula> |
| title_sort | five bonds to carbon through tri coordination in inline formula math display inline semantics mrow msub mrow mi al mi mrow mn 3 mn msub msubsup mi mathvariant normal c mi mn 3 mn mrow mo mo mo mo mn 0 mn mrow msubsup mrow semantics math inline formula |
| topic | <named-content content-type="inline-formula"><inline-formula><mml:math id="mm5"><mml:semantics><mml:mrow><mml:msub><mml:mrow><mml:mi>Al</mml:mi></mml:mrow><mml:mn>3</mml:mn></mml:msub><mml:msubsup><mml:mi mathvariant="normal">C</mml:mi><mml:mn>3</mml:mn><mml:mrow><mml:mo>−</mml:mo><mml:mo>/</mml:mo><mml:mn>0</mml:mn></mml:mrow></mml:msubsup></mml:mrow></mml:semantics></mml:math></inline-formula></named-content> five bonds to carbon anti-van’t Hoff-Le Bel σ-aromaticity π-aromaticity bonding |
| url | https://www.mdpi.com/2624-8549/5/2/76 |
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