Trifluoromethanesulphonato-O complexes of platinum(II) and palladium(II)

Reaction of chloroplatinum(II) and chloropalladium(II) complexes containing amine, pyridine (py), or phosphine ligands at or above room temperature with anhydrous CF3SO3H leads to formation of trifluoromethanesulphonato-O complexes, characterized spectroscopically. The complexes cis-[Pt(NH3)2(OSO2CF3)2], trans-[Pt(NH3)2Cl(OSO2CF3)], [Pt(en)Cl(OSO2CF3)], (en = 1,2-diaminoethane), [Pt(dppe)(OSO2CF3)2], [Pt(py)2Cl(OSO2CF3)], [Pt(terpy)(OSO2CF3)][CF3SO3], (terpy = 2,2′: 6′,2″-terpyridine), trans-[Pd(NH3)2Cl(OSO2CF3)], [Pd(en)(OSO2CF3)2], [Pd(bippy)(OSO2CF3)2](bipy = 2,2′-bipyridine), and [Pd(PPh3)2(OSO2CF3)2] were isolated. Aquation reactions of selected complexes showed that trifluoromethanesulphonate hydrolysis is rapid for complexes of both PtII and PdII. Bis(trifluoromethanesulphonato)platinum(II) complexes exhibit two consecutive rate processes, with k1/k2ca. 5, consistent with sequential hydrolysis of both anions. Preliminary investigations indicate that co-ordinated CF3SO3– in these complexes may be substituted even by neutral co-ordinating O-donor solvents.