The temperature-dependent pmr spectra of tris(N,N-disubstituted dithiocarbamato)metal(III) complexes, M(dtc)3, where = vanadium, manganese, chromium, gallium, and indium have been examined in noncoordinating solvents. All of the complexes are stereochemically nonrigid except for the chromium complex and kinetic parameters were determined for intramolecular metal-centered rearrangement by pmr line-broadening techniques. This rearrangement results in optical inversion and the trigonal twist mechanism has been assigned as the primary rearrangement pathway. The chromium complex is rigid up to 84 in CDCl3. The overall metal ion dependence on the rate of optical inversion is In, Ga, V > Mn > Cr. Trends in the rate and mechanism of rearrangement are considered in light of solid-state structural parameters and electronic configuration.