Supramolecular phosphate transfer catalysis by pillar[5]arene
| Autor: | Faruk Nome, Michelle Medeiros, Alex M. Manfredi, Luis García-Río, Rodrigo Montecinos, Daiane G. Liz, Borja Gómez-González |
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| Rok vydání: | 2016 |
| Předmět: |
Steric effects
010405 organic chemistry Chemistry Stereochemistry Metals and Alloys Cationic polymerization Supramolecular chemistry General Chemistry Pillararene 010402 general chemistry 01 natural sciences Catalysis 0104 chemical sciences Surfaces Coatings and Films Electronic Optical and Magnetic Materials Hydrolysis Molecular dynamics Reaction rate constant Polymer chemistry Materials Chemistry Ceramics and Composites |
| Zdroj: | Chemical Communications. 52:3167-3170 |
| ISSN: | 1364-548X 1359-7345 |
| DOI: | 10.1039/c5cc10214f |
| Popis: | A kinetic study on dinitrophenylphosphate monoester hydrolysis in the presence of a cationic pillararene, P5A, has been carried out. Formation of the supramolecular complex between phosphate ester and P5A has been studied by NMR showing complexation-induced upfield proton shifts indicative of aromatic ring inclusion in the pillararene cavity. Molecular dynamic calculations allow structure characterization for the 1 : 1 and 1 : 2 complexes. As a result of the supramolecular interaction both the acidity of DNPP and its hydrolysis rate constants are increased. Catalysis results from combination of both electrostatic stabilization reducing the negative electron density on the PO3(=) oxygens and monoester dianion destabilization by the steric effects of close NMe3(+) groups hindering the hydrogen-bonding with water and destabilising the monoester dianion. |
| Databáze: | OpenAIRE |
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