Influence of metal ion on chelate-aryl stacking interactions
Abstract
CCSD(T)/CBS and DFT methods are employed to study the stacking interactions of acetylacetonate-type (acac-type) chelates of nickel, palladium, and platinum with benzene. The strongest chelate-aryl stacking interactions are formed by nickel and palladium chelate, with interaction energies of -5.75 kcal mol(-1) and -5.73 kcal mol(-1), while the interaction of platinum chelate is weaker, with interaction energy of -5.36 kcal mol(-1). These interaction energies are significantly stronger than stacking of two benzenes, -2.73 kcal mol(-1). The strongest nickel and palladium chelate-aryl interactions are with benzene center above the metal area, while the strongest platinum chelate-aryl interaction is with the benzene center above the C2 atom of the acac-type chelate ring. These preferences arise from very different electrostatic potentials above the metal ions, ranging from very positive above nickel to slightly negative above platinum. While the differences in electrostatic potentials above... metal atoms cause different geometries with the most stable interaction among the three metals, the dispersion (correlation energy) component is the largest contribution to the total interaction energy for all three metals.
Keywords:
density functional theory / dispersion / electrostatic potentials / metal chelates / stacking interactionsSource:
International Journal of Quantum Chemistry, 2018, 118, 16Publisher:
- Wiley, Hoboken
Funding / projects:
- Noncovalent interactions of pi-systems and their role in molecular recognition (RS-MESTD-Basic Research (BR or ON)-172065)
- NPRP (Qatar National Research Fund, Qatar Foundation) [NPRP8-425-1-087]
- Qatar Foundation for Education, Science and Community Development
Note:
- Supplementary material: http://cherry.chem.bg.ac.rs/handle/123456789/3223
DOI: 10.1002/qua.25629
ISSN: 0020-7608
WoS: 000444678400003
Scopus: 2-s2.0-85045107826
Collections
Institution/Community
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Malenov, Dušan P. AU - Hall, Michael B. AU - Zarić, Snežana D. PY - 2018 UR - https://cherry.chem.bg.ac.rs/handle/123456789/2219 AB - CCSD(T)/CBS and DFT methods are employed to study the stacking interactions of acetylacetonate-type (acac-type) chelates of nickel, palladium, and platinum with benzene. The strongest chelate-aryl stacking interactions are formed by nickel and palladium chelate, with interaction energies of -5.75 kcal mol(-1) and -5.73 kcal mol(-1), while the interaction of platinum chelate is weaker, with interaction energy of -5.36 kcal mol(-1). These interaction energies are significantly stronger than stacking of two benzenes, -2.73 kcal mol(-1). The strongest nickel and palladium chelate-aryl interactions are with benzene center above the metal area, while the strongest platinum chelate-aryl interaction is with the benzene center above the C2 atom of the acac-type chelate ring. These preferences arise from very different electrostatic potentials above the metal ions, ranging from very positive above nickel to slightly negative above platinum. While the differences in electrostatic potentials above metal atoms cause different geometries with the most stable interaction among the three metals, the dispersion (correlation energy) component is the largest contribution to the total interaction energy for all three metals. PB - Wiley, Hoboken T2 - International Journal of Quantum Chemistry T1 - Influence of metal ion on chelate-aryl stacking interactions VL - 118 IS - 16 DO - 10.1002/qua.25629 ER -
@article{ author = "Malenov, Dušan P. and Hall, Michael B. and Zarić, Snežana D.", year = "2018", abstract = "CCSD(T)/CBS and DFT methods are employed to study the stacking interactions of acetylacetonate-type (acac-type) chelates of nickel, palladium, and platinum with benzene. The strongest chelate-aryl stacking interactions are formed by nickel and palladium chelate, with interaction energies of -5.75 kcal mol(-1) and -5.73 kcal mol(-1), while the interaction of platinum chelate is weaker, with interaction energy of -5.36 kcal mol(-1). These interaction energies are significantly stronger than stacking of two benzenes, -2.73 kcal mol(-1). The strongest nickel and palladium chelate-aryl interactions are with benzene center above the metal area, while the strongest platinum chelate-aryl interaction is with the benzene center above the C2 atom of the acac-type chelate ring. These preferences arise from very different electrostatic potentials above the metal ions, ranging from very positive above nickel to slightly negative above platinum. While the differences in electrostatic potentials above metal atoms cause different geometries with the most stable interaction among the three metals, the dispersion (correlation energy) component is the largest contribution to the total interaction energy for all three metals.", publisher = "Wiley, Hoboken", journal = "International Journal of Quantum Chemistry", title = "Influence of metal ion on chelate-aryl stacking interactions", volume = "118", number = "16", doi = "10.1002/qua.25629" }
Malenov, D. P., Hall, M. B.,& Zarić, S. D.. (2018). Influence of metal ion on chelate-aryl stacking interactions. in International Journal of Quantum Chemistry Wiley, Hoboken., 118(16). https://doi.org/10.1002/qua.25629
Malenov DP, Hall MB, Zarić SD. Influence of metal ion on chelate-aryl stacking interactions. in International Journal of Quantum Chemistry. 2018;118(16). doi:10.1002/qua.25629 .
Malenov, Dušan P., Hall, Michael B., Zarić, Snežana D., "Influence of metal ion on chelate-aryl stacking interactions" in International Journal of Quantum Chemistry, 118, no. 16 (2018), https://doi.org/10.1002/qua.25629 . .