Ion pair first and second acidities of some beta-diketones and aggregation of their lithium and cesium enediolates in THF.
Ion pair pK values were measured for three beta-diketones in THF, 1-3, with lithium and cesium counterions. The results showed variations with concentration indicative of aggregation of the metal enolates to dimers. Similarly, ion pair pK values could be determined for some of these metal enolates going to the corresponding dimetal dienediolates which were also found to form dimers. These equilibria are more complicated to analyze because aggregation affects both sides of the proton transfer equilibria. The results show that all of the species measured exist mostly as dimers at concentrations >0.01 M typical of most organic synthesis reactions and physical measurements. NMR measurements show that the enols of 1 and 2, which can undergo intramolecular hydrogen bonding, predominate in both THF and DMSO solutions, whereas 3, whose enols cannot be so stabilized, is mostly keto in THF but approximately equimolar enol and keto in DMSO. Dimerization of the monolithium salts is rapid on the NMR time scale but that of the dilithium salts is slow.
Facchetti
Antonio
A
Department of Chemistry, University of California, Berkeley, California 94720-1460, USA.
Streitwieser
Andrew
A
D000838:Anions / Q000737:chemistry; D002586:Cesium / Q000737:chemistry*; D005663:Furans / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D007477:Ions / Q000737:chemistry; D007659:Ketones / Q000138:chemical synthesis / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*
D000838:Anions; D005663:Furans; D007477:Ions; D007659:Ketones; D009942:Organometallic Compounds; D002586:Cesium; C018674:tetrahydrofuran; D008094:Lithium