The Sulfur Rich Fluorothiophosphate Dianions [S 5 P 2 F 2 ] 2- and [S 3 PF] 2- : Cluster and Chelation Control of P-S Heterolysis.

The sulfur rich difluoropentathiodiphosphate dianion [S 5 P 2 F 2 ] 2- , from fluoride addition to P 4 S 10 , has a somewhat checkered history and proves to be the main product of the reaction in acetonitrile. Its optimized synthesis, and structural characterization, as either a tetraphenylphosphonium or a tetrapropylammonium salt, [N n Pr 4 ] 2 [S 5 P 2 F 2 ] allows for the first coordination chemistry for this dianion. Reactions of [S 5 P 2 F 2 ] 2- with d 10 metal ions of zinc(II), and cadmium(II), and d 9 copper(II) resulted in a surprising diverse array of binding modes and structural motifs. In addition to the simple bis-chelate coordination of [S 5 P 2 F 2 ] 2- with zinc, cleavage of the P-S bond resulted in complexes with the unusual [S 3 PF] 2- fluorotrithiophosphate dianion. This was observed in two cluster complexes: a trinuclear cadmium complex with mixed [S 5 P 2 F 2 ] 2- /[S 3 PF] 2- ligands, [Cd 3 (S 5 P 2 F 2 ) 3 (S 3 PF) 2 ] 4- as well as an octanuclear copper cluster, [Cu 8 (S 3 PF) 6 ] 4- which form rapidly at room temperature. These new metal/sulfur/ligand clusters are of relevance to understanding multimetal binding to metallothionines, and to potential capping strategies for the condensed nanoparticulate cadmium chalcogenide semiconductors CdS and CdSe.