Previous kinetic and electrochemical studies of copper complexes with macrocyclic tetrathiaethers-such as 1,4,8,1 11-tetrathiacycloretradecane ([14]aneS(4))-have indicated that electron transfer and the accompanying conformational change occur sequentially to give rise to a dual-pathway mechanism. Under appropriate conditions, the conformational change itself may become rate-limiting, a condition known as "gated" electron transfer. We have recently hypothesized that the controlling conformational change involves inversion of two donor atoms, which suggests that "gated" behavior should be affected by appropriate steric constraints. In the current work, two derivatives of [14]aneS(4) have been synthesized in which one of the ethylene bridges has been replaced by either cis- or trans-1,2-cyclopentane. The resulting copper systems have been characterized in terms of their (CuL)-L-II/I potentials, the stabilities of their oxidized and reduced complexes, and their crystal structures. The electron self-exchange rate constants have been determined both by NMR line-broadening and by kinetic measurements of their rates of reduction and oxidation with six or seven counter reagents. All studies have been carried out at 25 degrees C, mu = 0.10 M (NaClO4 and/or Cu(ClO4)(2)), in aqueous solution. Both Cu(II/I) systems show evidence of a dual-pathway mechanism, and the electron self-exchange rate constants representative of both mechanistic pathways have been determined. The first-order rate constant for gated behavior has also been resolved for the Cu-I(trans-cyclopentane-[14 ] aneS(4)) complex, but only a limiting value can be established for the corresponding cycyclopentane system. The rate constants for both systems investigated in this work are compared to values previously determined for the Cu(II/I) systems with the parent [14]aneS(4) macrocycle and its derivatives involving phenylene and cis- or trans-cyclohexane substituents. The results are discussed in terms of the influence of the fused rings on the probable conformational changes accompanying the electron-transfer process.