Tetrel-Bond Interactions Involving Metallylenes TH<sub>2</sub> (T = Si, Ge, Sn, Pb): Dual Binding Behavior
The dual binding behavior of the metallylenes TH<sub>2</sub> (T = Si, Ge, Sn, Pb) with some selected Lewis acids (T’H<sub>3</sub>F, T’ = Si, Ge, Sn, Pb) and bases (N<sub>2</sub>, HCN, CO, and C<sub>6</sub>H<sub>6</sub>) has been investigate...
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| Format: | Article |
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MDPI AG
2023-03-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/6/2577 |
| _version_ | 1827748415535054848 |
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| author | Yishan Chen Lifeng Yao Fan Wang |
| author_facet | Yishan Chen Lifeng Yao Fan Wang |
| author_sort | Yishan Chen |
| collection | DOAJ |
| description | The dual binding behavior of the metallylenes TH<sub>2</sub> (T = Si, Ge, Sn, Pb) with some selected Lewis acids (T’H<sub>3</sub>F, T’ = Si, Ge, Sn, Pb) and bases (N<sub>2</sub>, HCN, CO, and C<sub>6</sub>H<sub>6</sub>) has been investigated by using the high-level quantum chemical method. Two types (type-A and type-B) of tetrel-bonded complexes can be formed for TH<sub>2</sub> due to their ambiphilic character. TH<sub>2</sub> act as Lewis bases in type-A complexes, and they act as Lewis acids in type-B ones. CO exhibits two binding modes in the type-B complexes, one of which is TH<sub>2</sub>···CO and the other is TH<sub>2</sub>···OC. The TH<sub>2</sub>···OC complexes possess a weaker binding strength than the other type-B complexes. The TH<sub>2</sub>···OC complexes are referred to as the type-B2 complexes, and the other type-B complexes are referred to as the type-B1 complexes. The type-A complexes exhibit a relatively weak binding strength with <i>E</i><sub>int</sub> (interaction energy) values ranging from –7.11 to –15.55 kJ/mol, and the type-B complexes have a broad range of <i>E</i><sub>int</sub> values ranging from −9.45 to −98.44 kJ/mol. The <i>E</i><sub>int</sub> values of the type-A and type-B1 complexes go in the order SiH<sub>2</sub> > GeH<sub>2</sub> > SnH<sub>2</sub> > PbH<sub>2</sub>. The AIM (atoms in molecules) analysis suggests that the tetrel bonds in type-A complexes are purely closed-shell interactions, and those in most type-B1 complexes have a partially covalent character. The EDA (Energy decomposition analysis) results indicate that the contribution values of the three energy terms go in the order electrostatic > dispersion > induction for the type-A and type-B2 complexes, and this order is electrostatic > induction > dispersion for the type-B1 complexes. |
| first_indexed | 2024-03-11T06:07:54Z |
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| id | doaj.art-f8b818133b54459eb87241692c821a52 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T06:07:54Z |
| publishDate | 2023-03-01 |
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| spelling | doaj.art-f8b818133b54459eb87241692c821a522023-11-17T12:52:16ZengMDPI AGMolecules1420-30492023-03-01286257710.3390/molecules28062577Tetrel-Bond Interactions Involving Metallylenes TH<sub>2</sub> (T = Si, Ge, Sn, Pb): Dual Binding BehaviorYishan Chen0Lifeng Yao1Fan Wang2School of Chemistry & Environmental Science, Qujing Normal University, Qujing 655011, ChinaSchool of Chemistry & Environmental Science, Qujing Normal University, Qujing 655011, ChinaSchool of Chemistry & Environmental Science, Qujing Normal University, Qujing 655011, ChinaThe dual binding behavior of the metallylenes TH<sub>2</sub> (T = Si, Ge, Sn, Pb) with some selected Lewis acids (T’H<sub>3</sub>F, T’ = Si, Ge, Sn, Pb) and bases (N<sub>2</sub>, HCN, CO, and C<sub>6</sub>H<sub>6</sub>) has been investigated by using the high-level quantum chemical method. Two types (type-A and type-B) of tetrel-bonded complexes can be formed for TH<sub>2</sub> due to their ambiphilic character. TH<sub>2</sub> act as Lewis bases in type-A complexes, and they act as Lewis acids in type-B ones. CO exhibits two binding modes in the type-B complexes, one of which is TH<sub>2</sub>···CO and the other is TH<sub>2</sub>···OC. The TH<sub>2</sub>···OC complexes possess a weaker binding strength than the other type-B complexes. The TH<sub>2</sub>···OC complexes are referred to as the type-B2 complexes, and the other type-B complexes are referred to as the type-B1 complexes. The type-A complexes exhibit a relatively weak binding strength with <i>E</i><sub>int</sub> (interaction energy) values ranging from –7.11 to –15.55 kJ/mol, and the type-B complexes have a broad range of <i>E</i><sub>int</sub> values ranging from −9.45 to −98.44 kJ/mol. The <i>E</i><sub>int</sub> values of the type-A and type-B1 complexes go in the order SiH<sub>2</sub> > GeH<sub>2</sub> > SnH<sub>2</sub> > PbH<sub>2</sub>. The AIM (atoms in molecules) analysis suggests that the tetrel bonds in type-A complexes are purely closed-shell interactions, and those in most type-B1 complexes have a partially covalent character. The EDA (Energy decomposition analysis) results indicate that the contribution values of the three energy terms go in the order electrostatic > dispersion > induction for the type-A and type-B2 complexes, and this order is electrostatic > induction > dispersion for the type-B1 complexes.https://www.mdpi.com/1420-3049/28/6/2577intermolecular interactionπ-holeσ-holeMEP surfacesNBO analysis |
| spellingShingle | Yishan Chen Lifeng Yao Fan Wang Tetrel-Bond Interactions Involving Metallylenes TH<sub>2</sub> (T = Si, Ge, Sn, Pb): Dual Binding Behavior Molecules intermolecular interaction π-hole σ-hole MEP surfaces NBO analysis |
| title | Tetrel-Bond Interactions Involving Metallylenes TH<sub>2</sub> (T = Si, Ge, Sn, Pb): Dual Binding Behavior |
| title_full | Tetrel-Bond Interactions Involving Metallylenes TH<sub>2</sub> (T = Si, Ge, Sn, Pb): Dual Binding Behavior |
| title_fullStr | Tetrel-Bond Interactions Involving Metallylenes TH<sub>2</sub> (T = Si, Ge, Sn, Pb): Dual Binding Behavior |
| title_full_unstemmed | Tetrel-Bond Interactions Involving Metallylenes TH<sub>2</sub> (T = Si, Ge, Sn, Pb): Dual Binding Behavior |
| title_short | Tetrel-Bond Interactions Involving Metallylenes TH<sub>2</sub> (T = Si, Ge, Sn, Pb): Dual Binding Behavior |
| title_sort | tetrel bond interactions involving metallylenes th sub 2 sub t si ge sn pb dual binding behavior |
| topic | intermolecular interaction π-hole σ-hole MEP surfaces NBO analysis |
| url | https://www.mdpi.com/1420-3049/28/6/2577 |
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