Metal Complexes of the Difluorodithiophosphate Ligand

Difluorodithiophosphato, F2PS2-, derivatives of monovalent Cu, Ag, and Au, divalent Mn, Fe, Co, Ni, Pd, Pt, Zn, Cd, and Hg, and trivalent Cr, Co, and Rh have been isolated and characterized. Many of these transition metal complexes are extremely volatile as exemplified by the Co(II) derivative which has a vapor pressure of 20 mm at 95 degrees. In contrast, the silver and copper(I) derivatives are nonvolatile and may have polymeric structures. All the difluorodithiophosphato complexes are susceptible to hydrolysis, but the rates vary widely from low in chromium(III) and nickel(II) to high in many of the bis derivatives. Chemically, the bis derivatives are the most reactive set and complex with donor molecules such as water, acetonitrile, phosphines, and anions. In this manner R3PPd(S2PF2)(2), R3AsPd(S2PF2)(2), (R3P)(2)Pd(S2PF2)(2), and Pd(S2PF2)(3)(-) have been isolated. These palladium complexes are believed to have square-planar form. Nitric oxide reacts with the bis derivatives of iron and cobalt to give the unusual nitrosyls (ON)(2)MS2PF2.