Synthesis and characterization of Ni(II), Zn(II), and Cd(II) complexes with dithiophosphonate derivatives

Ammonium salts of p-methoxyphenyldithiophosphonic acid O-alkyl esters (H3CO-C6H4-(RO)P(S)S-NH4+; R = C2H5, -H2CH2CH2CH2- and cyclopentyl) and their complexes with Ni2+, Cd2+, and Zn2+ were prepared. 2,4-Bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide, the so-called Lawesson reagent, was treated with the corresponding alcohol to give the O-alkyl ester of the acid. Dry NH3 was then purged through the solution of this ester to form the ammonium salt of the O-alkyl dithiophosphonic acids. Nickel complexes of these ligands were formed in acetic acid, while zinc and cadmium complexes were formed in water and an ethanol medium, respectively. According to the IR spectroscopic and 1, 13C, 31P NMR data, the geometry of the coordinated atoms was square planar with Ni2+ and tetrahedral with Zn2+ and Cd2+. Using an alkanediol, two dithiophosphonic acids were bridged, thus forming a ligand with four S atoms for coordination. The zinc and cadmium complexes of these tetradentate ligands were also synthesized