TY - JOUR
T1 - Solvent-induced Changes in the Selectivity of Solvolyses in Aqueous Alcohols and Related Mixtures
AU - Ta-Shma, Rachel
AU - Rappoport, Zvi
PY - 1992/1/1
Y1 - 1992/1/1
N2 - This chapter deals with the selectivity of an electrophilic carbon centre carrying a nucleofuge (RX) or of a solvolytically generated carbocation species (R+) toward the two nucleophilic solvent components. The chapter explains the solvent-induced changes in the selectivity values kA/kBin A–B mixtures (A and B being water (W), methanol (M), ethanol (E) or trifluoroethanol (TFE)). The chapter explains the selectivity of a single electrophilic species usually varies when the solvent composition is changed, owing to different responses of the individual rate constants kAand kBto the composition change. Solvent sorting around the electrophile does not explain the trends found for the variations of the individual rate constants. A proper analysis of changes in kA/kBmust be in terms of the changes in the individual rate constants. Because the selectivities are derived parameters, the importance of their solvent-induced changes as mechanistic probes will decrease if the values of the individual rate constants at various solvent compositions are known.
AB - This chapter deals with the selectivity of an electrophilic carbon centre carrying a nucleofuge (RX) or of a solvolytically generated carbocation species (R+) toward the two nucleophilic solvent components. The chapter explains the solvent-induced changes in the selectivity values kA/kBin A–B mixtures (A and B being water (W), methanol (M), ethanol (E) or trifluoroethanol (TFE)). The chapter explains the selectivity of a single electrophilic species usually varies when the solvent composition is changed, owing to different responses of the individual rate constants kAand kBto the composition change. Solvent sorting around the electrophile does not explain the trends found for the variations of the individual rate constants. A proper analysis of changes in kA/kBmust be in terms of the changes in the individual rate constants. Because the selectivities are derived parameters, the importance of their solvent-induced changes as mechanistic probes will decrease if the values of the individual rate constants at various solvent compositions are known.
UR - http://www.scopus.com/inward/record.url?scp=77956782843&partnerID=8YFLogxK
U2 - 10.1016/S0065-3160(08)60066-0
DO - 10.1016/S0065-3160(08)60066-0
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AN - SCOPUS:77956782843
SN - 0065-3160
VL - 27
SP - 239
EP - 291
JO - Advances in Physical Organic Chemistry
JF - Advances in Physical Organic Chemistry
IS - C
ER -