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Pseudo-first-order rate constants () have been measured spectrophotometrically for nucleophilic substitution reactions of 3,4-dinitrophenyl diphenylphosphinothioate 9 with alkali metal ethoxides (EtOM, M = Li, Na, K) in anhydrous ethanol at . The plot of vs. [EtOM] is linear for the reaction of 9 with EtOK. However, the plot curves downwardly for those with EtOLi and EtONa while it curves upwardly for the one with EtOK in the presence of 18-crown-6-ether (18C6). Dissection of into and (i.e., the second-order rate constant for the reaction with dissociated and ion-paired EtOM, respectively) has revealed that the reactivity increases in the order , indicating that the reaction is inhibited by and ions but is catalyzed by 18C6-crowned ion. The reactivity order found for the reactions of 9 contrasts to that reported previously for the corresponding reactions of 1, i.e., > > > , indicating that the effect of changing the electrophilic center from P=O to P=S on the role of ions is significant. A four-membered cyclic transition-state has been proposed to account for the ion effects found in this study, e.g., the polarizable sulfur atom of the P=S bond in 9 interacts strongly with the soft 18C6-crowned ion while it interacts weakly with the hard and ions.

bulletin of the korean chemical society

Alkali Metal Ion Catalysis and Inhibition in Nucleophilic Substitution Reactions of 3,4-Dinitrophenyl Diphenylphosphinothioate with Alkali Metal Ethoxides in Anhydrous Ethanol: Effect of Changing Electrophilic Center from P=O to P=S