title: Lithium and Cesium Ion-Pair Acidities of Dibenzyl Ketone. Aggregation of Lithium and Cesium Ion Pairs of the Enolate Ion and Dianion(1)(,).
abstract: Spectral study of the cesium and lithium enolates of dibenzyl ketone (DBK) showed that both salts exist as contact ion pairs in THF solutions. The spectral data for the dicesium salt of DBK indicate that it exists as triple ions in which both cations are in contact with the dianion. The dilithium salt of DBK forms triple ions of two types in THF: in one, both cations are in contact with the DBK dianion, in the other, one of the lithium cations is solvent-separated. Evidence for dimerization of the ion pairs was obtained for both lithium and cesium enolates of DBK from UV-vis spectral (blue shift of the absorbance band at higher concentrations) and acidity (the decrease of pK at higher concentrations) studies. The dimerization constant for the cesium enolate of DBK obtained from the acidity data (3.5 x 10(3) M(-)(1)) is considered to be more accurate than that from the spectral analysis (1.7 x 10(3) M(-)(1)). The lithium enolate is much less dimerized than its cesium counterpart with a dimerization constant from acidity data of 4.2 x 10(2) M(-)(1). The first and second cesium pK values of DBK are 18.07 and 33.70, respectively, compared to the first lithium pK of 11.62.
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720-1460.
authors.forename: Roustam
authors.initials: R
authors.lastname: Gareyev
authors.forename: James C.
authors.initials: JC
authors.lastname: Ciula
authors.forename: Andrew
authors.initials: A
authors.lastname: Streitwieser