DINUCLEAR AND TRINUCLEAR COMPLEXES OF WS4 2- WITH TRICARBONYLRHENIUM(I) AND TRICARBONYLMANGANESE(I) FRAGMENTS - STRUCTURE, SPECTROSCOPY, AND ELECTROCHEMISTRY

The reaction of (NEt4)(2)WS4 with two equivalents of M(CO)(5)(O3SCF3), M = Mn or Re, in acetonitrile yielded the crystallographically charac terized neutral compounds [(CH3CN)(OC)(3)M(mu-S2WS2)M(CO)(3)(NCCH3)]. The individual molecules are chiral and contain WS4 and MS2(CO)(3)(CH3 CN) moieties in approximately tetrahedral and octahedral configuration s, respectively. Vibrational and electronic absorption spectra are in agreement with the crystal structure, comparable results were obtained for trinuclear complexes [(L)(OC)(3)Re(mu-S2WS2)Re(CO)(3)(L)](NEt4)(2 ), L = Cl- or CN-, and for the dinuclear systems [(WS4) Re(CO)(3)(CH3C N)] (NEt4) and [(WS4)Re(CO)(3)Cl] (NEt4)(2). Electrochemical processes are irreversible due to the lability of acetonitrile or chloride liga nds in corresponding complexes, however, the cyanide compound [(NC)(OC )(3)Re(mu-S2WS2)Re(CO)(3)(CN)](2-) showed reversible one-electron redu ction to a first tetrathiotungstate(V) species as detected by UV/Vis/I r spectroelectrochemistry.