A potentiometric titration study of the complexation of metal ions (M+) by 4,7,13,16- tetraoxa-1,10-diazabicyclo[8.8.5] tricosane (C22C5) at 298.2 K and I = 0.05 (NEt4ClO4) yields log(K/dm3 mol-1) =6.07 and 5.36, 7.55 and 5.95, 6.26 and 7.56, 5.5 and 6.66, 4.57 and 5.16, and 8.14 and 14.51 when M+ = Li+, Na+, K+, Rb +, Cs+ and Ag+, respectively, where the first and second magnitudes of each pair refer to the stability constant (K) for [M(C22C5)]+ in acetonitrile and ropylene carbonate solvent, respectively. A 7Li n.m.r. tudy yields kd (298.2 K) = 428 s-1, ∆ Hd ‡ = 24.7 kJ mol-1 and ∆ Sd ‡ = -111 J K-1 mol-1 for the monomolecular decomplexation of Li+ from [Li(C22C5)]+, and kc(298.2 K) = 9.83×107 dm3 mol-1 s-1 for the complexation process in propylene carbonate. These data are compared with those for related systems and are discussed in terms of the factors affecting cryptate stability and lability.
The Determination of Exchange Equilibrium Constants of Alkali Metal Ions and the Purification of Potassium Chloride