Novel cyclopentadienyl (Cp)-alkali metal complexes 1-M and 2-M (M = Li, Na, K), in which the Cp ring is annelated with two bicyclo[2.2.2]octene units and substituted with a phenyl group for 1 and a tert-butyl group for 2, were synthesized, and their structures and dynamic behaviors were investigated by means of X-ray crystallography, dynamic C-13 NMR, and DFT calculations. The X-ray crystallography results indicated that 1-Li, 1-Na, and 2-Na. form monomeric contact ion pairs (CIP) with three THF molecules coordinated to the metal atom. Also, in THF-d(8), all of the 1-M and 2-M form monomeric CIP in the ground state. However, variable-temperature 13C NMR measurements of 1-M and 2-M in THF-d8 demonstrated dynamic behavior in which the metal ion exchanges positions between the upper and lower faces of the Cp ring. From a study of the concentration dependence of the dynamic behavior, the exchange was found to proceed principally as an intramolecular process at concentration ranges lower than 0.2 M. The experimentally observed DeltaG(double dagger) values for the intramolecular exchange process for all the 1-M and 2-M (except for 2-Li, whose intramolecular process was too slow to observe) were found to be quite similar in THF-d(8) solution and to fall within the range of 12-14 kcal mol(-1). Within this range, a tendency was observed for the DeltaG(double dagger) values to increase as the size of the metal decreased. Theoretical calculations (B3LYP/6-31 G(d)) afforded considerably large values as the gas-phase dissociation energy for 1-M (162.7 kcal mol(-1) for M = Li; 131.6 kcal mol(-1) for M = Na; 110.9 kcal mol(-1) for M = K) and for 2-M (170.0 kcal mol(-1) for M = Li; 137.5 kcal mol(-1) for M = Na; 115.4 kcal mol(-1) for M = K). These values should be compensated for by a decrease in the solvation energies for the metal ions with increasing size, as exemplified by the calculated solvation energy for M+(Me2O)4, which serves as a model for metal ions solvated with four molecules of THF (-122.9 kcal mol(-1) for M = Li; -94.7 kcal mol(-1) for M = Na; -67.7 kcal mol(-1) for M = K). This compensation results in a small difference in the overall energy for dissociation of 1-M or 2-M in ethereal solutions, thus supporting the similar DeltaG(double dagger) values observed for the intramolecular metal exchange.