Ditopic dithiocarbamate ligands for the production of trinuclear species

Abstract

Reactions of group 10 transition metals with the ditopic ligand dipicolyldithiocarbamate (DPDTC) were performed. Thus, 1:2 reactions of [Ni(CH3COO)2], [Pd(COD)Cl2] or [Pt(COD)Cl2] with DPDTC produced monomeric complexes of the type [M(κ2-SCS-DPDTC)2, M = Ni (1), Pd (2) or Pt (3)] with the dithiocarbamate ligand (DTC) coordinated in a typical chelate κ2-SCS fashion. Interestingly, the reaction of [NiCl2] with DPDTC, under similar conditions, afforded the organic compound 2-(pyridin-2-ylmethyl)imidazo[1,5-a]pyri-dine-3(2 H)-thione (4) as unique product. In order to prove the ditopic nature of the ligand DPDTC, complex [Pd(κ2-SCS-DPDTC)2] (2) was further reacted with [ZnCl2] in a 1:2 M ratio to yield the trinuclear complex [Cl2Zn(κ2-NN-DPDTC-SCS-κ2)Pd(κ2-SCS-DPDTC-NN-κ2)ZnCl2] (5). The molecular structures of all compounds were determinate by typical analytical techniques including the unequivocal determination of all structures by single crystal X-ray diffraction analysis. As expected, complexes 1–3 are isostructural, and the metal centres exhibiting slightly distorted square-planar geometries. While in 5, the trinuclear nature of the complex in confirmed exhibiting a nice combination of tetrahedral-square planar-tetrahedral geometries for the Zn-Pd-Zn centres respectively.