Covalent vs. Dative Bonding in Carbon Monoxide and Other 10-Valence-Electron Diatomics
Valence bond theory (VB) was used to determine the extent and driving forces for covalent vs. dative bonding in 10-valence-electron diatomic molecules N<sub>2</sub>, CO, NO<sup>+</sup>, CN<sup>−</sup>, P<sub>2</sub>, SiS, PS<sup>+</sup>, an...
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2024-11-01
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| author | Khadija Rizwan John Morrison Galbraith |
| author_facet | Khadija Rizwan John Morrison Galbraith |
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| description | Valence bond theory (VB) was used to determine the extent and driving forces for covalent vs. dative bonding in 10-valence-electron diatomic molecules N<sub>2</sub>, CO, NO<sup>+</sup>, CN<sup>−</sup>, P<sub>2</sub>, SiS, PS<sup>+</sup>, and SiP<sup>−</sup>. VBSCF calculations were performed at the CCSD(T)/cc-pVDZ optimized geometries. The full triply bonded system included 20 VB structures. A separation of the σ and π space allowed for a subdivision of the full 20 structure set into sets of 8 and 3 for the π and σ systems, respectively. The smaller structure sets allowed for a more focused look at each type of bond. In situ bond energies for σ bonds, individual π bonds, the π system, and triple bonds follow expected trends. Our data shows that N<sub>2</sub> and P<sub>2</sub> have three covalent bonds whereas CO and SiS contain two covalent and one dative bond, and charged species NO<sup>+</sup>, CN<sup>−</sup>, PS<sup>+</sup>, and SiP<sup>−</sup> are a mixture of N<sub>2</sub> and CO type electronic arrangements, resulting in a nearly equal charge distribution. Dative bonds prefer to be in the π position due to enhanced σ covalency and π resonance. Both σ and π resonance energies depend on a balance of ionic strength, orbital compactness, σ constraints, and bond directionality. Resonance energy is a major contributor to bond strength, making up more than 50% of the π bonds in SiS and PS<sup>+</sup> (charge-shift bonds), and is greater than charge transfer in dative bonds. |
| format | Article |
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| spelling | doaj-art-7cd434f66939482c849d38a1bb8ae6b62025-08-20T02:48:01ZengMDPI AGMolecules1420-30492024-11-012922539610.3390/molecules29225396Covalent vs. Dative Bonding in Carbon Monoxide and Other 10-Valence-Electron DiatomicsKhadija Rizwan0John Morrison Galbraith1Department of Chemistry, Biochemistry and Physics, Marist College, 3399 North Road, Poughkeepsie, NY 12601, USADepartment of Chemistry, Biochemistry and Physics, Marist College, 3399 North Road, Poughkeepsie, NY 12601, USAValence bond theory (VB) was used to determine the extent and driving forces for covalent vs. dative bonding in 10-valence-electron diatomic molecules N<sub>2</sub>, CO, NO<sup>+</sup>, CN<sup>−</sup>, P<sub>2</sub>, SiS, PS<sup>+</sup>, and SiP<sup>−</sup>. VBSCF calculations were performed at the CCSD(T)/cc-pVDZ optimized geometries. The full triply bonded system included 20 VB structures. A separation of the σ and π space allowed for a subdivision of the full 20 structure set into sets of 8 and 3 for the π and σ systems, respectively. The smaller structure sets allowed for a more focused look at each type of bond. In situ bond energies for σ bonds, individual π bonds, the π system, and triple bonds follow expected trends. Our data shows that N<sub>2</sub> and P<sub>2</sub> have three covalent bonds whereas CO and SiS contain two covalent and one dative bond, and charged species NO<sup>+</sup>, CN<sup>−</sup>, PS<sup>+</sup>, and SiP<sup>−</sup> are a mixture of N<sub>2</sub> and CO type electronic arrangements, resulting in a nearly equal charge distribution. Dative bonds prefer to be in the π position due to enhanced σ covalency and π resonance. Both σ and π resonance energies depend on a balance of ionic strength, orbital compactness, σ constraints, and bond directionality. Resonance energy is a major contributor to bond strength, making up more than 50% of the π bonds in SiS and PS<sup>+</sup> (charge-shift bonds), and is greater than charge transfer in dative bonds.https://www.mdpi.com/1420-3049/29/22/5396valence bond theorydative bondscharge-shift bondingresonance energy |
| spellingShingle | Khadija Rizwan John Morrison Galbraith Covalent vs. Dative Bonding in Carbon Monoxide and Other 10-Valence-Electron Diatomics Molecules valence bond theory dative bonds charge-shift bonding resonance energy |
| title | Covalent vs. Dative Bonding in Carbon Monoxide and Other 10-Valence-Electron Diatomics |
| title_full | Covalent vs. Dative Bonding in Carbon Monoxide and Other 10-Valence-Electron Diatomics |
| title_fullStr | Covalent vs. Dative Bonding in Carbon Monoxide and Other 10-Valence-Electron Diatomics |
| title_full_unstemmed | Covalent vs. Dative Bonding in Carbon Monoxide and Other 10-Valence-Electron Diatomics |
| title_short | Covalent vs. Dative Bonding in Carbon Monoxide and Other 10-Valence-Electron Diatomics |
| title_sort | covalent vs dative bonding in carbon monoxide and other 10 valence electron diatomics |
| topic | valence bond theory dative bonds charge-shift bonding resonance energy |
| url | https://www.mdpi.com/1420-3049/29/22/5396 |
| work_keys_str_mv | AT khadijarizwan covalentvsdativebondingincarbonmonoxideandother10valenceelectrondiatomics AT johnmorrisongalbraith covalentvsdativebondingincarbonmonoxideandother10valenceelectrondiatomics |