The rate constants for ring inversion (k(r.i.)) and bond shift (k(b.s.)) in 1 and 2 were determined by dynamic NMR spectrometry while the rate constants for bond shift and intramolecular charge transfer (k(c)) were determined for 1(2-)/2K(+) and 2(2-)/2K(+). These processes were modeled by HF/3-21G((*)) ab initio molecular orbital calculations of the ground states and of several transition states for 3, 4, 3(2-), 4(2-), 3(2-)/2K(+), and 4(2-)/2K(+). The results indicate that k(r.i.) and k(b.s.) are ca. 2.5 times greater (at 240 and 280 K, respectively) for 2 compared to 1 due to larger steric repulsions in the ground state of 2. Contrariwise, k(b.s.) and k(c) are 1.7 and 166 times greater, respectively, at 280 K for 1(2-)/2K(+) than for 2(2-)/2K(+). These differences are attributed to less twisting and therefore greater pi delocalization between the cyclooctatetraenyl rings and the aryl ring in the bond shift and charge-transfer transition states of 1(2-) compared to 2(2-). The greater difference between 12- and 22- for k(c) compared to k(b.s.) is postulated to result from looser ion pairing in the charge-transfer transition state relative to the bond shift transition state.