A heteropolynuclear R-2[S2WS2Re(O)(Cl)S2WS2] (R = PPh4 and Et4N) complex. The first example of a tetrathiometalate ligand co-ordinated to an oxo-metal core

A solution of [ReOCl3(PPh3)(2)] in benzene reacts with solid (NH4)(2)WS4, i n the presence of traces of H2O, to give [ReOCl(WS4)(2)](2-), isolated as i ts PPh4 (1) and NEt4 (2) salts. Both (1) and (2) exhibit nu(Re=O) at ca. 93 0, nu(Re-Cl) at ca. 330 nu(W=S)(t) at ca. 495 and nu(W-S-Re) bridging vibra tion at ca. 460 cm(-1). The FAB mass spectrum of (1) shows a peak for [ReO( WS4)(2)](+) (m/z = 826 amu) in the positive mode and that for {PPh4[ReOCl(W S4)]}(-) (m/z = 889 amu) in the negative mode, confirming the suggested com position. This is the second example of a d(2) metal ion forming a tetrathi ometalate complex and also the first example of an oxometal ion (excepting those of W and Mo) forming a molecular complex with tetrathio- tungstate or -molybdate ligands.