Structure and coordination in mono and dinuclear Zn(II)-pyrrolidine dithiocarbamate complexes

The structures of the chelate Zn(PDTC)₂ and its dimeric form Zn₂(PDTC)₄ are investigated theoretically at B3LYP/cc-pVDZ level. The natural bond orbital (NBO) analysis has been performed to explore the metal–ligand coordination of these chelates. In Zn(PDTC)₂, the sulfur atoms mainly use 3p sub-shells to coordinate with mixed (4s + 4p _x  + 4p _y  + 4p _z ) orbital of zinc having sp ³ hybridization. In Zn₂(PDTC)₄, each zinc atom coordinates with one terminal and two bridging PDTC ligands. The contribution of bridging sulfur atoms in chelation is much more than terminal sulfurs. The bridging sulfur atoms use 3s and 3p sub-shells to coordinate with 4s and 4p sub-shells of metal center zinc. The charge transfer interactions between sulfur and metal center involving 4d, 5s, and 5p sub-shells of zinc are much feeble compared to those involving 4s and 4p sub-shells of zinc.