6533b854fe1ef96bd12afc7f

RESEARCH PRODUCT

High yield synthesis of trinuclear [M3S4X3(diphos)3]+ (M=Mo, W; X=Cl, Br and diphos=dmpe, dppe) molecular clusters from solid state materials. Synthesis and structure of [W3S4H3(dppe)3](BPh4)

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The excision of polymeric {M 3 S 7 X 4 } x (M=Mo, W; X=Cl, 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 [M 3 S 4 X 3 (diphos) 3 ] + (M=Mo, W; X=Cl, Br and diphos=dmpe, dppe) in high yields. Following this strategy, the cluster cations [Mo 3 S 4 Br 3 (dmpe) 3 ] + and [W 3 S 4 Br 3 (dppe) 3 ] + have been prepared for the first time. This last tungsten cluster has proved to be a useful synthon for the synthesis of the hydride derivative [W 3 S 4 H 3 (dppe) 3 ] + in moderate yields. The crystal structure of [W 3 S 4 H 3 (dppe) 3 ](BPh 4 ) consists of a equilateral tungsten triangle with one capping and three bridging sulfur atoms defining a incomplete W 3 S 4 cuboidal unit in which the tungsten and the sulfur atoms occupy adjacent vertex of a cube with a metal atom missing. The hydride 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 diphosphine phosphorus atoms, located one above and one bellow the M 3 plane resulting in two different 31 P{ 1 H} NMR signals. Electrochemical studies for all trinuclear clusters reported show one quasi reversible and one irreversible reduction process.