Multi-Center Covalency: Revisiting the Nature of Anion-pi Interactions

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Publikace nespadá pod Filozofickou fakultu, ale pod Středoevropský technologický institut. Oficiální stránka publikace je na webu muni.cz.
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FOROUTANNEJAD Cina BADRI Zahra MAREK Radek

Rok publikování 2015
Druh Článek v odborném periodiku
Časopis / Zdroj Physical Chemistry Chemical Physics
Fakulta / Pracoviště MU

Středoevropský technologický institut

Citace
www DOI: 10.1039/C5CP05777A
Doi http://dx.doi.org/10.1039/C5CP05777A
Obor Fyzikální chemie a teoretická chemie
Klíčová slova anion-pi; bonding; interacting quantum atoms; covalency; exchange-correlation
Přiložené soubory
Popis Exploring the nature of anion–pi bonding by means of the Quantum Theory of Atoms in Molecules (QTAIM) and an energy decomposition scheme on the basis of Interacting Quantum Atoms (IQA) theory led us to conclude that these non-classical interactions benefit from “multi-center covalency” far more than from the electrostatics. Comparing anion–pi systems to closely related covalent anion–sigma complexes reveals that the anion–pi systems benefit from an extensive degree of electron sharing between the anions and all atoms of the pi-rings. Besides, decomposition of the binding energy into classical (electrostatics) and non-classical (exchange–correlation) components demonstrates that in contrast to previous reports, the anion–pi complexes are local minima, if and only if the non-classical contribution to binding energy surpasses that of the electrostatics. This suggests that the stable anion–pi complexes with the anions atop the pi-rings might be prepared with pi-systems that benefit more from the exchange–correlation term, such as extended pi-systems, but not with strong electrostatic pi-receptors. This conclusion is in line with the tendency of strong pi-acids to form the sigma-complexes with more covalent character instead of the pi-complexes.
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