The stereochemistry and dynamics of MoO2(acac)(2) in benzene, chloroform, and toluene were investigated by variable temperature NMR, density functional theory (SOGGA11-X, B3LYP), and ab (MP2) methods, In solution, an equilibrium between two chiral enantiomers with C-2 symmetry was identified, A-cis-MoO2(acac)(2) and Delta-cis-MoO2(acac)(2). The two enantiomers are: connected via achiral cis transition states that switch the enantiomeric conformations via a Ray-Dutt, Bailar, and a newly described racemization twisting mechanism. All three mechanisms have similar calculated activation energies. Activation parameters E-a, Delta H-double dagger, and Delta S-double dagger were experimentally determined for the exchange process, With a small, negative Delta S-double dagger, and a positive Delta H-double dagger of 68.1 kJ mol(-1) in benzene, 54.9 kJ mol(-1) in chloroform, and 60.6 kJ mor(-1) in toluene, in reasonable general agreement with the Calculations. Trans configurations of MoO2(acac)(2) are very much higher in energy than cis and are not relevant in the temperature range experimentally studied, 243-340 K. The enantiomers interconvert within seconds near room temperature and much faster at elevated temperatures. Racemization will thus prevent the use of enantiomerically pure MoO2(acac)(2) for chiral catalysis under practical conditions.