Journal of the American Chemical Society

Origin of the Bell-Shaped. alpha.-Effect-Solvent Composition Plots. pKa-Solvent Dependence of the. alpha.-Effect at a Phosphorus Center

RM Tarkka, E Buncel

文献索引：Tarkka, Richard M.; Buncel, Erwin Journal of the American Chemical Society, 1995 , vol. 117, # 5 p. 1503 - 1507

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被引用次数: 85

摘要

Abstract: The rates of reaction of the" a" nucleophile, 2, 3-butanedione monoximate (Ox-), and the" normal" nucleophile, 4-chlorophenoxide (4-ClPhO-), with the phosphorus ester, p- nitrophenyl diphenylphosphinate (PNPDPP), were measured in DMSO-H20 mixtures at 25.0" C. Addition of small quantities of DMSO (up to ca. 10 mol%) to the aqueous solvent led to a decrease in the second-order rate constants of reaction for both nucleophiles. ...