The reactions of M(ClO4)(2)center dot xH(2)O (M = Ni(II) or Cd(II)) and m-bis[bis(1-pyrazolyl)methyl]benzene (L-m) in the presence of triethylamine lead to the formation of hydroxide-bridged cubane compounds of the formula [M-4(mu(3)-OH)(4)(mu-L-m)(2)(solvent)(4)] (ClO4)(4), where solvent = dimethylformamide, water, acetone. In the solid state the metal centers are in an octahedral coordination environment, two sites are occupied by pyrazolyl nitrogens from L-m, three sites are occupied by bridging hydroxides, and one site contains a weakly coordinated solvent molecule. A series of multinuclear, two-dimerisional and variable-temperature experiments showed that the cadmium(II) compound in acetonitrile-d(3) has C-2 symmetry and undergoes an unusual dynamic process at higher temperatures (Delta G(Lm)(double dagger) = 15.8 +/- 0.8 kcal/mol at 25 degrees C) that equilibrates the pyrazolyl rings, the hydroxide hydrogens, and cadmium(II) centers. The proposed mechanism for this process combines two motions in the semirigid L-m ligand termed the "Columbia Twist and Flip:" twisting of the pyrazolyl rings along the C-pz-C-methine bond and 180 degrees ring flip of the phenylene spacer along the C-ph-C-methine bond. This dynamic process was also followed using the spin saturation method, as was the exchange of the hydroxide hydrogens with the trace water present in acetonitrile-d3. The nickel(II) analogue, as shown by magnetic susceptibility and electron paramagnetic resonance measurements, has an S = 4 ground state, and the nickel(II) centers are ferromagnetically coupled with strongly nonaxial zero-field splitting parameters. Depending on the Ni-O-Ni angles two types of interactions are observed: J(1) = 9.1 cm(-1) (97.9 to 99.5 degrees) and J(2) = 2.1 cm(-1) (from 100.3 to 101.5 degrees). "Broken symmetry" density functional theory calculations performed on a model of the nickel(H) compound support these observations.