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Ion association and reactivity of the alkali metal salts of alkanoic acids in dipolar aprotic solvents
Author(s) -
Crescenzi Manuela,
Galli Carlo,
Mandolini Luigi
Publication year - 1990
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610030703
Subject(s) - chemistry , reactivity (psychology) , alkali metal , inorganic chemistry , ion , dimethylformamide , caesium , ring (chemistry) , metal , ion association , reaction rate constant , organic chemistry , kinetics , solvent , pathology , physics , quantum mechanics , medicine , alternative medicine
The effect of added alkali metal perchlorates on the rate of lactonization of ω‐bromoalkanoate ions was investigated in 99% dimethyl sulphoxide (four‐membered ring formation) and in dimethylformamide (DMF) (four‐ and sixteen‐membered ring formation). In all cases the effect of the added metal salts is rate depressing, as a result of the lower reactivity of metal ion‐associated species relative to the free ions. Ion‐pairing association constants were determined, but the reactivity of ion pairs were so low as to elude direct measurement in most cases. Evidence was also obtained for the formation of ion triplets with Li + in DMF. The relevance of the present results in connection with the ‘caesium effect’ is briefly discussed.