Origin of the Enhanced Binding Capability toward Axial Nitrogen Bases of Ni(II) Porphyrins Bearing Electron-Withdrawing Substituents: An Electronic Structure and Bond Energy Analysis
| Autor: | Evert Jan Baerends, Giampaolo Ricciardi, Mario Amati, Angela Rosa |
|---|---|
| Přispěvatelé: | AIMMS, Theoretical Chemistry |
| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
010405 organic chemistry
Chemistry Charge density chemistry.chemical_element Electronic structure 010402 general chemistry Ring (chemistry) 01 natural sciences Porphyrin 0104 chemical sciences Inorganic Chemistry Metal Crystallography chemistry.chemical_compound Nickel visual_art Polar effect visual_art.visual_art_medium Physical and Theoretical Chemistry Bond energy |
| Zdroj: | Inorganic Chemistry, 59(16), 11528-11541. American Chemical Society Amati, M, Baerends, E J, Ricciardi, G & Rosa, A 2020, ' Origin of the Enhanced Binding Capability toward Axial Nitrogen Bases of Ni(II) Porphyrins Bearing Electron-Withdrawing Substituents : An Electronic Structure and Bond Energy Analysis ', Inorganic Chemistry, vol. 59, no. 16, pp. 11528-11541 . https://doi.org/10.1021/acs.inorgchem.0c01327 |
| ISSN: | 0020-1669 |
| Popis: | Axial coordination to metalloporphyrins is important in many biological and catalytic processes. Experiments found the axial coordination of nitrogenous bases to nickel(II) porphyrins to be strongly favored by electron-withdrawing substituents such as perfluorophenyls at the meso carbon positions. Careful analysis of the electronic structure reveals that the natural explanation in terms of density change of the nickel(II) porphyrin system (in particular the metal), does not apply. Electron density changes, by the assumed inductive or polarizing effects on the metal or on the porphyrin ring system, are slight. The effect is caused by a remarkable through-space electric field effect on the metalloporphyrin system, originating from the charge distribution inside the perfluorphenyl groups (mostly the C-F dipoles). |
| Databáze: | OpenAIRE |
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