Electrochemical Synthesis and Characterization of Cobalt(II), Cobalt(III), and Nickel(II) Complexes with Pyrimidine‐2‐thionato Ligands

The electrochemical oxidation of anodic metal (cobalt and nickel) in acetonitrile solutions of the appropriate pyrimidine‐2‐thione derivatives (RpymSH, where R = 4‐CF 3 , 4,6‐CF 3 Me, 4,6‐MePh, 4,6‐CF 3 Ph, 4,6‐Ph 2 ) afforded complexes of composition [M(RpymS) 2 ], M = Co, Ni or [Co(RpymS) 3 ]. When 2,2′‐bipyridine (bipy) or 1,10‐phenanthroline (phen) was added to the electrolytic cell, adducts of cobalt(II) and nickel(II) compounds with these coligands were obtained: [M(RpymS) 2 bipy] and [M(RpymS) 2 phen]. All of the compounds were characterized by microanalysis, electronic, vibrational spectroscopy and FAB mass spectrometry, and, in the cases of the compounds [Co(RpymS) 3 ], by 1 H and 13 C, NMR spectroscopy. The compound [Co(4‐CF 3 pymS) 3 ] was also characterized by X‐ray diffraction. The crystal structure consists of monomeric molecules in which the central CoS 3 N 3 unit has a slightly distorted octahedral coordination with the ligands adopting a meridional disposition.