The Structure-Stability Relationship of the Metal Ion Complexes of Unsaturated Compounds. IV. Argentation Equilibria of Alkenyl Alkyl Ethers

Abstract

Abstract The equilibrium constants, K, for the formation of 1 : 1 Ag+ - alkenyl alkyl ether complexes were measured in the temperature range 10 to 30°C by the gas chromatographic method. It has been found (1) that cis isomers have the values of K several times greater than those of the corresponding trans isomers, (2) that the K-value tends to diminish with the increasing degree of β-substitutions, (3) that, in a series of cis ethers, K increases as the β-alkyl substituent becomes bulkier, and (4) that the variation of the alkoxy groups causes little change in the K-value. The difference in the K-values between the cis and trans complexes is found to be ascribable mainly to their difference in the enthalpy changes, ΔH, accompanying the complexation. These trends have been discussed on a thermodynamic ground in comparison with those already noted for olefins.