A Study on Auto-Catalysis and Product Inhibition: A Nucleophilic Aromatic Substitution Reaction Catalysed within the Cavity of an Octanuclear Coordination Cage
CHEMISTRY-A EUROPEAN JOURNAL(2024)
摘要
The ability of an octanuclear cubic coordination cage to catalyse a nucleophilic aromatic substitution reaction on a cavity-bound guest was studied with 2,4-dinitrofluorobenzene (DNFB) as the guest/substrate. It was found that DNFB undergoes a catalysed reaction with hydroxide ions within the cavity of the cubic cage (in aqueous buffer solution, pH 8.6). The rate enhancement of kcat/kuncat was determined to be 22, with cavity binding of the guest being required for catalysis to occur. The product, 2,4-dinitrophenolate (DNP), remained bound within the cavity due to electrostatic stabilisation and exerts two apparently contradictory effects: it initially auto-catalyses the reaction when present at low concentrations, but at higher concentrations inhibits catalysis when a pair of DNP guests block the cavity. When encapsulated, the UV/Vis absorption spectrum of DNP is red-shifted when compared to the spectrum of free DNP in aqueous solution. Further investigations using other aromatic guests determined that a similar red-shift on cavity binding also occurred for 4-nitrophenolate (4NP) at pH 8.6. The red-shift was used to determine the stoichiometry of guest binding of DNP and 4NP within the cage cavity, which was confirmed by structural analysis with X-ray crystallography; and was also used to perform catalytic kinetic studies in the solution-state. An octanuclear cubic coordination cage catalyses the nucleophilic aromatic substitution reaction of a cavity-bound guest, 2,4-dinitrofluorobenzene (DNFB). The product 2,4-dinitrophenolate (DNP) remained bound within the cavity, providing both autocatalysis in the early stages and inhibition in the late stages of the reaction. A red-shift in the UV/Vis spectrum revealed 1 : 2 host to guest binding, this was confirmed by X-ray crystallography analysis. image
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关键词
supramolecular chemistry,host-guest systems,coordination cage,catalysis,crystallography
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