The Sulfur Rich Fluorothiophosphate Dianions [S5P2F2]2- and [S3PF]2- : Cluster and Chelation Control of P-S Heterolysis

The sulfur rich difluoropentathiodiphosphate dianion [S5P2F2](2-), from fluoride addition to P4S10, 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, [(NPr4)-Pr-n](2)[S5P2F2] allows for the first coordination chemistry for this dianion. Reactions of [S5P2F2](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 [S5P2F2](2-) with zinc, cleavage of the P-S bond resulted in complexes with the unusual [S3PF](2-) fluorotrithiophosphate dianion. This was observed in two cluster complexes: a trinuclear cadmium complex with mixed [S5P2F2](2-)/[S3PF](2-) ligands, [Cd-3(S5P2F2)(3)(S3PF)(2)](4-) as well as an octanuclear copper cluster, [Cu-8(S3PF)(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.

Automated summary

This article describes the synthesis and structural characterization of [S5P2F2](2-) and its reactions with metal ions such as zinc, cadmium, and copper. The results show a diverse array of binding modes and structural motifs, which are relevant to understanding multimetal binding to metallothionines and potential capping strategies for CdS and CdSe nanoparticles.