Fluorotrithiophosphate Abstraction from the Difluoropentathiodiphosphate Dianion: d⁸ and d⁶ Complexes of [η²-S₃PF]^2–

Coordinative heterolysis of the difluoropentathiodiphosphate dianion [S5P2F2]2– results in the formal elimination of [S2PF] by complexes of the group 10 divalent metals nickel, palladium, and platinum. The remaining fragment of this cleavage, [S3PF]2– coordinates as an η2-ligand. Several complexes with this novel fluorotrithiophosphate were characterized structurally and spectroscopically with X-ray diffraction (XRD), infrared (IR) spectroscopy, and 31P and 19F nuclear magnetic resonance (NMR). In addition to mononuclear η2 chelate complexes, bridging complexes with η2-μ2-S3PF 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 [S2P(O)SMe]2–. Alternatively hydrolysis can also lead to a binuclear Ni2(dppe)2(S3PF)(S2POF) complex. Divalent ruthenium π-aryl’s form fluorotrithiophosphate complexes rapidly at room temperature to give bridged dimers with complete chloride substitution.