Malonaldehyde-like Systems: BeF<sub>2</sub> Clusters—A Subtle Balance between Hydrogen Bonds, Beryllium Bonds, and Resonance
The stability of malonaldehyde is governed by intramolecular hydrogen bonds (IMHBs) as well as in malonaldehyde-like systems where oxygen is replaced by N or S at any of the basic sites. As beryllium bonds have been shown to strongly cooperate with hydrogen bonds, this work explores at the high leve...
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| Format: | Article |
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MDPI AG
2022-02-01
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| Online Access: | https://www.mdpi.com/2413-4155/4/1/7 |
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| author | M. Merced Montero-Campillo Otilia Mó Manuel Yáñez |
| author_facet | M. Merced Montero-Campillo Otilia Mó Manuel Yáñez |
| author_sort | M. Merced Montero-Campillo |
| collection | DOAJ |
| container_title | Sci |
| description | The stability of malonaldehyde is governed by intramolecular hydrogen bonds (IMHBs) as well as in malonaldehyde-like systems where oxygen is replaced by N or S at any of the basic sites. As beryllium bonds have been shown to strongly cooperate with hydrogen bonds, this work explores at the high level ab initio G4 level of theory the effect of including this non-covalent interaction in the system through its association with BeF<sub>2</sub>. Although malonaldehyde follows the expected trends, where the formation of a pseudocyclic form is favored also when IMHB and Be bonds are present, the subtle balance between both non-covalent interactions leads to some surprising results when other heteroatoms are involved, to the point that interaction energies can be much larger than expected or even cyclization is not favored. A complete analysis using different computational tools gives an answer to those cases escaping the predictable trends. |
| format | Article |
| id | doaj-art-eaca10c933fa4be8a234df8ca8a78250 |
| institution | Directory of Open Access Journals |
| issn | 2413-4155 |
| language | English |
| publishDate | 2022-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| spelling | doaj-art-eaca10c933fa4be8a234df8ca8a782502025-08-19T22:32:52ZengMDPI AGSci2413-41552022-02-0141710.3390/sci4010007Malonaldehyde-like Systems: BeF<sub>2</sub> Clusters—A Subtle Balance between Hydrogen Bonds, Beryllium Bonds, and ResonanceM. Merced Montero-Campillo0Otilia Mó1Manuel Yáñez2Departamento de Química, Módulo 13, Facultad de Ciencias and Institute of Advanced Chemical Sciences (IAdChem), Universidad Autónoma de Madrid, Campus de Excelencia UAM-CSIC, Cantoblanco, 28049 Madrid, SpainDepartamento de Química, Módulo 13, Facultad de Ciencias and Institute of Advanced Chemical Sciences (IAdChem), Universidad Autónoma de Madrid, Campus de Excelencia UAM-CSIC, Cantoblanco, 28049 Madrid, SpainDepartamento de Química, Módulo 13, Facultad de Ciencias and Institute of Advanced Chemical Sciences (IAdChem), Universidad Autónoma de Madrid, Campus de Excelencia UAM-CSIC, Cantoblanco, 28049 Madrid, SpainThe stability of malonaldehyde is governed by intramolecular hydrogen bonds (IMHBs) as well as in malonaldehyde-like systems where oxygen is replaced by N or S at any of the basic sites. As beryllium bonds have been shown to strongly cooperate with hydrogen bonds, this work explores at the high level ab initio G4 level of theory the effect of including this non-covalent interaction in the system through its association with BeF<sub>2</sub>. Although malonaldehyde follows the expected trends, where the formation of a pseudocyclic form is favored also when IMHB and Be bonds are present, the subtle balance between both non-covalent interactions leads to some surprising results when other heteroatoms are involved, to the point that interaction energies can be much larger than expected or even cyclization is not favored. A complete analysis using different computational tools gives an answer to those cases escaping the predictable trends.https://www.mdpi.com/2413-4155/4/1/7intramolecular hydrogen-bondsberyllium bondscooperativityresonance |
| spellingShingle | M. Merced Montero-Campillo Otilia Mó Manuel Yáñez Malonaldehyde-like Systems: BeF<sub>2</sub> Clusters—A Subtle Balance between Hydrogen Bonds, Beryllium Bonds, and Resonance intramolecular hydrogen-bonds beryllium bonds cooperativity resonance |
| title | Malonaldehyde-like Systems: BeF<sub>2</sub> Clusters—A Subtle Balance between Hydrogen Bonds, Beryllium Bonds, and Resonance |
| title_full | Malonaldehyde-like Systems: BeF<sub>2</sub> Clusters—A Subtle Balance between Hydrogen Bonds, Beryllium Bonds, and Resonance |
| title_fullStr | Malonaldehyde-like Systems: BeF<sub>2</sub> Clusters—A Subtle Balance between Hydrogen Bonds, Beryllium Bonds, and Resonance |
| title_full_unstemmed | Malonaldehyde-like Systems: BeF<sub>2</sub> Clusters—A Subtle Balance between Hydrogen Bonds, Beryllium Bonds, and Resonance |
| title_short | Malonaldehyde-like Systems: BeF<sub>2</sub> Clusters—A Subtle Balance between Hydrogen Bonds, Beryllium Bonds, and Resonance |
| title_sort | malonaldehyde like systems bef sub 2 sub clusters a subtle balance between hydrogen bonds beryllium bonds and resonance |
| topic | intramolecular hydrogen-bonds beryllium bonds cooperativity resonance |
| url | https://www.mdpi.com/2413-4155/4/1/7 |
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