Complex formation kinetics have been measured for solvated Cu(II) reacting with an entire series of cyclohexanediyl derivatives of the 14-membered cyclic tetrathiaether [14]aneS(4) (1,4,8,11-tetrathiacyclotetradecane) using stopped-flow spectrophotometry. In this ligand series, cis- or trans-1,2-cyclohexanediyl has been substituted for one or both of the ethylene bridges in [14]aneS(4) resulting in two monocyclohexanediyl and five dicyclohexanediyl derivatives. The complex formation rate constants in 80% methanol-20% water (by weight) for the reaction of Cu(II) with the parent [14]aneS(4) ligand and all seven cyclohexanediyl-substituted derivatives at 25.0 +/- 0.2 degrees C, mu = 0.10 M (HClO4), are found to Lie within the narrow range of (2-5) x 10(4) M(-1) s(-1). The consistency in these values implies that the introduction of cyclohexanediyl substituents does not induce significant steric effects relative to the first two bond formation steps. Using solvated Hg(II) ion as a ligand scavenger, the first-order dissociation rate constants have been measured independently under the same conditions and are found to vary over a range of 10(4). The ratios of the formation and dissociation rate constants are shown to agree closely with the previously determined stability constants, thereby establishing the fact that the kinetically observed products are the thermodynamically stable species. Strain optimization calculations indicate that one of the ligand conformational changes, which must precede the first Cu-S bond rupture, represents the most unfavorable step in the dissociation process. The rate constants for direct mercury(II) exchange provide additional insight into the dissociation behavior of the Cu(II) complexes.