High yield syntheiss of trinuclear [M_3S_4X_3(diphos)_3]~+ (M=Mo, W; X=Cl,Br and diphos=dmpe,dppe) molecular clusters from solid state materials. Synthesis and structure of [W_3S_4H_3(dppe)_3](BPh_4)

摘要

The excision of polymeric {M3S7X4}" (M = Mo, W; X= CI, Br) cluster phases with diphosphines (dmpe, dppe) in acetonitrile affords a one step general synthetic route for the preparation of trinuclear molecular clusters with formula [MJS4X3(diphos)J+ (M = Mo, W; X= CI, Br and diphos = dmpe, dppe) in high yields. Following this strategy, the cluster cations [MoJS4Br3(dmpe)J+ and lWJS4~r3(dppe)J+ha~e been.pr~pared for the first time: This last tun~sten cluster has proved to be a useful synthon for the synthesIs of the hydrIde derivatIve [W3S4H3(dppe)J+ m moderate yields. The crystal structure of [W3S4H3(dppe)3](BPh4) consists of a equilateral tungsten triangle with one capping and three bridging sulfur atom& defining a incomplete W 3S4 cuboidal unit in which the tungsten and the sulfur atoms occupy adjacent vertex of a cube with a metal atom missing. The hydtide ligand occupies the outer position of the metal in a pseudo-octahedral environment. The other two outer positions on each metal are occupied by the dfphosphine phosphorus atoms, located one above and one bellow the M3 plane resulting in two different 3IP{IH} NMR signats. Electrochemical studies for all trinuctear clusters reported show one quasi reversible and one irreversible reduction process.