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• W2078674106 abstract "The kinetics of the title reactions were determined in 50% DMSO−50% water (v/v) at 20 °C; n-BuS-, HOCH2CH2S-, and MeO2CCH2S- were used as thiolate ions. The reactions with the thiolate ions gave rise to two separate kinetic processes. The first refers to rapid, reversible attachment of RS- to the substrate leading to a tetrahedral intermediate ( , ), the second to the conversion of the intermediate to products ( ). In most cases all of the rate constants ( , , and ) could be determined. In combination with results from previous studies, a detailed discussion regarding the effects of activating substituents and leaving groups on rate and equilibrium constants as well as on intrinsic rate constants is presented. The reaction with OH- only allowed a determination of for nucleophilic attack on the substrate; in this case the tetrahedral intermediate remains at steady-state levels under all conditions." @default.
• W2078674106 created "2016-06-24" @default.
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• W2078674106 date "2001-02-14" @default.
• W2078674106 modified "2023-09-29" @default.
• W2078674106 title "Unraveling Structure−Reactivity Relationships in S_NV Reactions: Kinetics of the Reactions of Methoxybenzylidenemalononitrile, 2-(Methylthiobenzylidene)-1,3-indandione, 2-(Benzylthiobenzylidene)-1,3-indandione, and Methyl β-Methylthio-α-nitrocinnamate with OH^- and Thiolate Ions in Aqueous DMSO" @default.
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• W2078674106 doi "https://doi.org/10.1021/ja003536t" @default.
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