Divergent Behavior in the Chemistry of Metal-Bis(dithiolene) Complexes Appended with Peripheral Aliphatic Butyl Chains

Metal-bis(dithiolene) complexes derived from Ni(II), Co(II), Pd(II), Pt(II) and Au(III), bearing butyl aliphatic chains have been synthesized, and fully characterized by a variety of spectroscopic techniques including NMR, UV-vis, IR, HRMS, CV, and X-ray diffraction studies. This comparative study made possible to establish that the Co(II) species appear to be dimeric in the solid state as well as in solution. On the other hand, the coordination complexes based on Ni(II), Pd(II), Pt(II) and Au(III), feature a monomeric structure in both solution and solid state. These metal-bis(dithiolene) complexes are remarkably stable in solution and, in stark contrast to precedents in the literature, they retain their square planar geometry even in presence of pyridine derivatives reported for their apical binding on metal-bis(dithiolene) complexes.