Divalent transition metal complexes of alkylpyridyl derivatized dmit ligands

Abstract

The two new bis-alkylpyridyl substituted dmit ligands, 4,5-bis(2-pyridylmethylsulfanyl)-1,3-dithiole-2-thione (bpmdmit) and 4,5-bis(2-pyridylethylsulfanyl)-1,3-dithiole-2-thione (bpedmit), and some of their transition metal complexes have been prepared. Two basic structural types for the complexes MX 2L (M=Ni, Co, Cu, Pd; L=bpmdmit or bpedmit; X=Cl or Br) were determined by X-ray crystallography. The cobalt(II) and the nickel(II) complexes CoBr 2(bpmdmit) and NiCl 2(bpmdmit) show octahedral geometries around the metal ions with coordination to the metal ions by the pyridyl nitrogen atoms and the thioether sulfur atoms of the ligand and cis coordination of the halide ions. By contrast, only the pyridyl nitrogen atom of the ligands in the copper(II) and the palladium(II) complexes, CuCl 2(bpedmit) and PdCl 2(bpedmit), are coordinated to the metal ions to give essentially square planar metal environments. The copper complex was isolated as both green and purple crystals. However, the X-ray structures of both forms are similar, and show a dimeric arrangement with bis-μ-chloride bridges between the copper ions in the dimeric units. The green crystals contain two molecules of acetonitrile in the unit cell, however these do not interact with the metal ions. The geometry of the copper ions in the green form deviates most from centrosymmetric square planar geometry and this is consistent with the observed colour. Apart from the colour, the solids can be distinguished in the solid state by EPR spectroscopy since they give different rhombic signals. UV–Vis and EPR spectroscopy show that in solution the structures of the purple and green forms of CuCl 2(bpedmit) are identical, as expected.