The complete series of alcoholic derivatives for the 13- through 16-membered macrocyclic tetrathia ethers, in which a single -OH group is attached to the central carbon of a trimethylene bridge, has now been synthesized. The derivatized ligands show a marked improvement in aqueous solubility, permitting the measurement of both the Cu(II) complex stability constants (K-CuIIL') and the corresponding formation (k(f)) and dissociation (k(d)) rate constants in aqueous solution at 25 degrees C. Insofar as possible, the K-CuIIL', k(f), and k(d) values were determined from independent measurements to assess the level of consistency between them. The (CuL)-L-II/I formal potentials for complexes of the OH-substituted ligands have also been determined, permitting the calculation of the stability constants for the (CuL)-L-I complexes. Except for the potential measurements, all values were determined in the presence of both 0.10 and 1.0 M perchlorate to assess the uniformity of anion adduct effects upon the various kinetic and thermodynamic values. All values for the alcoholic derivatives are compared to the corresponding parameters determined previously for the unsubstituted macrocycles-for which, due to solubility limitations, the formation kinetic data had to be extrapolated to aqueous conditions from measurements made in methanol-water mixtures. In general, the substitution of an -OH group on the ligand backbone results in a 5-8-fold decrease in the k(f) values. This decrease in complex formation rate is attributed to the influence of hydrogen bonding between the -OH group and the surrounding solvent molecules upon the preferred ligand conformation in water. The k(f) values for both series of ligands are consistent with a mechanism in which the closure of the first chelate ring is the rate-determining step. The effect of -OH substitution upon the k(d) values is somewhat variable but tends to be less pronounced. The OH-substituted 14-membered macrocycle appears to be somewhat unique from the standpoint that the Cu(II) complex is twice as stable as the unsubstituted analogue, whereas all other -OH derivatives show a decrease in (CuL)-L-II stability. Also included in the current study are measurements on the Cu(II) complex formed with a water-soluble oxathiane derivative of the 12-membered macrocyclic tetrathia ether (oxathiane-[12]aneS(4)).