Pentacoordinate Carbon Atoms in a Ferrocene Dication Derivative—[Fe(Si<sub>2</sub>-<i>η</i><sup>5</sup>-C<sub>5</sub>H<sub>2</sub>)<sub>2</sub>]<sup>2+</sup>
Pentacoordinate carbon atoms are theoretically predicted here in a ferrocene dication derivative in the eclipsed-(<b>1</b>; <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>C</mi>...
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MDPI AG
2022-09-01
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| Online Access: | https://www.mdpi.com/2624-8549/4/4/74 |
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| author | Shilpa Shajan Jin-Chang Guo Aland Sinjari Krishnan Thirumoorthy Venkatesan S. Thimmakondu |
| author_facet | Shilpa Shajan Jin-Chang Guo Aland Sinjari Krishnan Thirumoorthy Venkatesan S. Thimmakondu |
| author_sort | Shilpa Shajan |
| collection | DOAJ |
| description | Pentacoordinate carbon atoms are theoretically predicted here in a ferrocene dication derivative in the eclipsed-(<b>1</b>; <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>C</mi><mrow><mn>2</mn><mi>v</mi></mrow></msub></semantics></math></inline-formula>), gauche-(<b>2</b>; <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>C</mi><mn>2</mn></msub></semantics></math></inline-formula>) and staggered-[Fe(Si<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>-<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mi>η</mi><mn>5</mn></msup></semantics></math></inline-formula>-C<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>5</mn></msub></semantics></math></inline-formula>H<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>)<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>]<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mrow></mrow><mrow><mn>2</mn><mo>+</mo></mrow></msup></semantics></math></inline-formula>(<b>3</b>; <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>C</mi><mrow><mn>2</mn><mi>h</mi></mrow></msub></semantics></math></inline-formula>) forms for the first time. Energetically, the relative energy gaps for <b>2</b> and <b>3</b> range from −3.06 to 16.74 and −2.78 to 40.34 kJ mol<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mrow></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msup></semantics></math></inline-formula>, respectively, when compared to the singlet electronic state of <b>1</b> at different levels. The planar tetracoordinate carbon (ptC) atom in the ligand Si<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>C<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>5</mn></msub></semantics></math></inline-formula>H<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula> becomes a pentacoordinate carbon upon complexation. The ligand with a ptC atom was predicted to be both a thermodynamically and kinetically stable molecule by some of us in our earlier theoretical works. Natural bond orbital and adaptive natural density partitioning analyses confirm the pentacoordinate nature of carbon in these three complexes (<b>1</b>–<b>3</b>). Although they are hypothetical at the moment, they support the idea of “hypercoordinate metallocenes” within organometallic chemistry. Moreover, ab initio molecular dynamics simulations carried out at 298 K temperature for 2000 fs suggest that these molecules are kinetically stable. |
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| last_indexed | 2024-03-09T17:12:36Z |
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| spelling | doaj.art-b07137718b504d33a864d39ab2532e412023-11-24T13:58:15ZengMDPI AGChemistry2624-85492022-09-01441092110010.3390/chemistry4040074Pentacoordinate Carbon Atoms in a Ferrocene Dication Derivative—[Fe(Si<sub>2</sub>-<i>η</i><sup>5</sup>-C<sub>5</sub>H<sub>2</sub>)<sub>2</sub>]<sup>2+</sup>Shilpa Shajan0Jin-Chang Guo1Aland Sinjari2Krishnan Thirumoorthy3Venkatesan S. Thimmakondu4School of Advanced Sciences, Vellore Institute of Technology, Vellore 632 014, Tamil Nadu, IndiaNanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006, ChinaSchool of Mathematics, Biological, Exercise & Physical Sciences, San Diego Miramar College, San Diego, CA 92126-2910, USASchool 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, USAPentacoordinate carbon atoms are theoretically predicted here in a ferrocene dication derivative in the eclipsed-(<b>1</b>; <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>C</mi><mrow><mn>2</mn><mi>v</mi></mrow></msub></semantics></math></inline-formula>), gauche-(<b>2</b>; <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>C</mi><mn>2</mn></msub></semantics></math></inline-formula>) and staggered-[Fe(Si<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>-<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mi>η</mi><mn>5</mn></msup></semantics></math></inline-formula>-C<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>5</mn></msub></semantics></math></inline-formula>H<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>)<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>]<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mrow></mrow><mrow><mn>2</mn><mo>+</mo></mrow></msup></semantics></math></inline-formula>(<b>3</b>; <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>C</mi><mrow><mn>2</mn><mi>h</mi></mrow></msub></semantics></math></inline-formula>) forms for the first time. Energetically, the relative energy gaps for <b>2</b> and <b>3</b> range from −3.06 to 16.74 and −2.78 to 40.34 kJ mol<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mrow></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msup></semantics></math></inline-formula>, respectively, when compared to the singlet electronic state of <b>1</b> at different levels. The planar tetracoordinate carbon (ptC) atom in the ligand Si<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>C<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>5</mn></msub></semantics></math></inline-formula>H<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula> becomes a pentacoordinate carbon upon complexation. The ligand with a ptC atom was predicted to be both a thermodynamically and kinetically stable molecule by some of us in our earlier theoretical works. Natural bond orbital and adaptive natural density partitioning analyses confirm the pentacoordinate nature of carbon in these three complexes (<b>1</b>–<b>3</b>). Although they are hypothetical at the moment, they support the idea of “hypercoordinate metallocenes” within organometallic chemistry. Moreover, ab initio molecular dynamics simulations carried out at 298 K temperature for 2000 fs suggest that these molecules are kinetically stable.https://www.mdpi.com/2624-8549/4/4/74ferrocenehypercoordinated-metallocene[Fe(Si<sub>2</sub>-<i>η</i><sup>5</sup>-C<sub>5</sub>H<sub>2</sub>)<sub>2</sub>]<sup>2+</sup>pentacoordinate carbonplanar tetracoordinate carbonkinetic stability |
| spellingShingle | Shilpa Shajan Jin-Chang Guo Aland Sinjari Krishnan Thirumoorthy Venkatesan S. Thimmakondu Pentacoordinate Carbon Atoms in a Ferrocene Dication Derivative—[Fe(Si<sub>2</sub>-<i>η</i><sup>5</sup>-C<sub>5</sub>H<sub>2</sub>)<sub>2</sub>]<sup>2+</sup> Chemistry ferrocene hypercoordinated-metallocene [Fe(Si<sub>2</sub>-<i>η</i><sup>5</sup>-C<sub>5</sub>H<sub>2</sub>)<sub>2</sub>]<sup>2+</sup> pentacoordinate carbon planar tetracoordinate carbon kinetic stability |
| title | Pentacoordinate Carbon Atoms in a Ferrocene Dication Derivative—[Fe(Si<sub>2</sub>-<i>η</i><sup>5</sup>-C<sub>5</sub>H<sub>2</sub>)<sub>2</sub>]<sup>2+</sup> |
| title_full | Pentacoordinate Carbon Atoms in a Ferrocene Dication Derivative—[Fe(Si<sub>2</sub>-<i>η</i><sup>5</sup>-C<sub>5</sub>H<sub>2</sub>)<sub>2</sub>]<sup>2+</sup> |
| title_fullStr | Pentacoordinate Carbon Atoms in a Ferrocene Dication Derivative—[Fe(Si<sub>2</sub>-<i>η</i><sup>5</sup>-C<sub>5</sub>H<sub>2</sub>)<sub>2</sub>]<sup>2+</sup> |
| title_full_unstemmed | Pentacoordinate Carbon Atoms in a Ferrocene Dication Derivative—[Fe(Si<sub>2</sub>-<i>η</i><sup>5</sup>-C<sub>5</sub>H<sub>2</sub>)<sub>2</sub>]<sup>2+</sup> |
| title_short | Pentacoordinate Carbon Atoms in a Ferrocene Dication Derivative—[Fe(Si<sub>2</sub>-<i>η</i><sup>5</sup>-C<sub>5</sub>H<sub>2</sub>)<sub>2</sub>]<sup>2+</sup> |
| title_sort | pentacoordinate carbon atoms in a ferrocene dication derivative fe si sub 2 sub i η i sup 5 sup c sub 5 sub h sub 2 sub sub 2 sub sup 2 sup |
| topic | ferrocene hypercoordinated-metallocene [Fe(Si<sub>2</sub>-<i>η</i><sup>5</sup>-C<sub>5</sub>H<sub>2</sub>)<sub>2</sub>]<sup>2+</sup> pentacoordinate carbon planar tetracoordinate carbon kinetic stability |
| url | https://www.mdpi.com/2624-8549/4/4/74 |
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