In a systematic approach to comparing the molecular structure and bonding in homoleptic transition-metal and actinide complexes, a series of dithiocarbamates, M(SCNPr) (M = Ti, Zr, Hf, Th, U, Np), have been synthesized. These complexes have been characterized through spectroscopic and X-ray crystallographic analysis, and their bonding has been examined using density functional theory calculations. Computational results indicate that the covalent character associated with the M-S bonds shows the trend of Hf < Zr < Th < Ti < U ≈ Np.