The absolute magnitude of an "entatic" (constrained) state effect has never been quantitatively demonstrated. In the current study, we have examined the electron-transfer kinetics for five closely related copper(II/I) complexes formed with all possible diastereomers of [14]aneS(4) (1,4,X,11-tetrathiacyclotetradecane) in which both ethylene bridges have been replaced by cis- or trans-1,2-cyclohexane. The crystal structures of all five Cu(II) complexes and a representative Cu(I) complex have been established by X-ray diffraction. For each complex. the cross-reaction rate constants have been determined with six different oxidants and reductants in aqueous solution at 25 degreesC, mu = 0.10 M. The value of the electron self-exchange rate constant (k(11)) has then been calculated from each cross reaction rate constant using the Marcus cross relation. All five Cu(II/I) systems show evidence of a dual-pathway square scheme mechanism for which the two individual kit values have been evaluated. In combination with similar values previously determined for the parent complex, Cu-II/I([14]aneS(4)), and corresponding complexes with the two related monocyclohexanediyl derivatives, we now have evaluated a total of 16 self-exchange rate constants which span nearly 6 orders of magnitude for these 8 closely related Cu(II/I) systems. Application of the stability constants for the formation of the corresponding 16 metastable intermediates-as previously determined by rapid-scan cyclic voltammetry-makes it possible to calculate the specific electron self-exchange rate constants representing the reaction of each of the strained intermediate species exchanging electrons with their stable redox partners-the first time that calculations of this type have been possible. All but three of these 16 specific self-exchange rate constants fall within-or very close to-the range of 10(5)-10(6) M-1 s(-1), values which are characteristic of the most labile Cu(II/I) systems previously reported, including the blue copper proteins. The results of the current investigation provide the first unequivocal demonstration of the efficacy of the entatic state concept as applied to Cu(II/I) systems.