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0343640299
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note
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Abbreviations: DNPP, 2,4-dinitrophenyl phosphate; MDNPP, methyl 2,4-dinitrophenyl phosphate; BDNPP, bis-2,4-dinitrophenyl phosphate; pNPP, p-nitrophenyl phosphate; pNPPS, p-nitrophenyl phosphorothioate.
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a of the 2,4-dinitrophenol leaving group renders bond scission without proton transfer favorable.
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It is important to note that the hydrolysis of ethyl phosphate dianion could still occur via the alkyl phosphate monoanion and hydroxide ion in a fashion consistent with the classical mechanism (eq 1). Such a pathway would be favored if the advantage from proton transfer to the leaving group and the modest increase in reactivity for hydroxide ion relative to water compensated for the lower concentrations of these species relative to the alkyl phosphate dianion and water. This possibility is currently under investigation. Regardless, the observed thio effect suggests that the proton does not remain on the transferred phosphoryl group in the transition state, as postulated in the substrate-assisted catalysis mechanism.
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