Fluorotrithiophosphate Abstraction from the Difluoropentathiodiphosphate Dianion: d 8 and d 6 Complexes of [η 2 -S 3 PF] 2 .

Coordinative heterolysis of the difluoropentathiodiphosphate dianion [S 5 P 2 F 2 ] 2- results in the formal elimination of [S 2 PF] by complexes of the group 10 divalent metals nickel, palladium, and platinum. The remaining fragment of this cleavage, [S 3 PF] 2- coordinates as an η 2 -ligand. Several complexes with this novel fluorotrithiophosphate were characterized structurally and spectroscopically with X-ray diffraction (XRD), infrared (IR) spectroscopy, and 31 P and 19 F nuclear magnetic resonance (NMR). In addition to mononuclear η 2 chelate complexes, bridging complexes with η 2 -μ 2 -S 3 PF configurations result in binuclear nickel and ruthenium adducts. Facile methylation with methyl triflate of the uncoordinated sulfur atom leads to a complex with the methylthiofluorodithiophosphate ligand in a cationic complex, which hydrolyses with loss of fluoride to give complexed [S 2 P(O)SMe] 2- . Alternatively hydrolysis can also lead to a binuclear Ni 2 (dppe) 2 (S 3 PF)(S 2 POF) complex. Divalent ruthenium π-aryl's form fluorotrithiophosphate complexes rapidly at room temperature to give bridged dimers with complete chloride substitution.