Coordination Chemistry and QTAIM Analysis of Homoleptic Dithiocarbamate Complexes, M(S2CNiPr2)4 (M = Ti, Zr, Hf, Th, U, Np)

In a systematic approach to comparing the molecular structure and bonding in homoleptic transition-metal and actinide complexes, a series of dithiocarbamates, M­(S2CNiPr2)4 (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.