ALKALI-METAL ION CATALYSIS AND INHIBITION IN NUCLEOPHILIC DISPLACEMENT-REACTIONS OF PHOSPHORUS-BASED, SULFUR-BASED AND CARBON-BASED ESTERS

Interesting and varied metal-ion effects were observed in the reaction of ethoxide ion with a series of carbon-, phosphorus-, and sulfur-bas ed esters. Catalysis and inhibition were analysed in terms of ground-s tate and transition-state stabilization, leading to insight into the d ifferential role of metal-ion solvation in the transition state. The r esults are discussed with reference to the Eisenman theory of ion-exch ange selectivity and to ab initio studies of transition-state stabiliz ation.