A novel low-temperature intramolecular exchange was detected by C-13 NMR spectrometry in the Na+ and K+ salts of the title compound. The process causes the pairwise exchange in the dianion ring of C-2", C-3", and C-4" with C-8", C-7", and C-6", respectively. The free energy of activation (DeltaG(double dagger) (exch)) for the dipotassium Salt (2(2-)/2K(+)) in THF-d(8) at 230 K is 12.6 kcal mol(-1). Two key questions are addressed: (1) Why are these carbons anisochronous and (2) what is the mechanism of exchange? NMR data for 1-cyclooctatetraenylnaph-thalenedipotassium (3(2-)/2K(+)) as well as ab initio HF/3-21G(*) calculations for 3, 3(2-), and 3(2-)/2K(+) indicate that the nonequivalence is due to both slow rotation across a barrier at which the naphthalene and COT(2-)rings are approximately coplanar and slow inversion of the neutral COT ring. This results in the noteworthy circumstance of diastereotopic carbons being observed in a molecule that does not possess either a stereogenic or a prostereogenic center. Comparison of DeltaG*(exch) and DeltaG(BS)(double dagger) for 2(2-)/2K(+) with the corresponding values for 2(2-)/2Na(+) and 2(2-)/2Li(+) and of DeltaG(exch)(double dagger) with DeltaG(double dagger) for ring inversion in 1,4-dicyclooctatetraenylnaphthalene leads to the conclusion that COT2- ring rotation and COT ring inversion both contribute to exchange in 2(2-)/2K(+) in a 3:1 ratio, but that exchange occurs exclusively by ring rotation in 2(2-)/2Li(+). The latter result is attributed to looser ion pairing in the dilithium (and disodium) salts.