Zwei- und dreikemige Organometallkomplexe (ReS4)[MCl(C5Me5)], M = Rh, Ir, und (μ-WS4)[IrCl(C5Me5)]2 / Dinuclear and Trinuclear Organometallic Complexes (ReS4)[MCl(C5Me5)], M = Rh, Ir, and (μ-WS4)[IrCl(C5Me5)]2

Abstract

The reactions of tetrathiorhenate(VII) or tetrathiotungstate(VI) with [MCl2(C5Me5)]2, M = Rh or Ir, yield the neutral title compounds of which (ReS4)[RhCl(C5Me5)] and (μ- WS4)[IrCl(C5Me5)]2 could be crystallographically characterized. The molecules contain nearly tetrahedral M′S4 units and rhodium(III) or iridium(III) centers with piano stool geometry. Weak intermolecular (M)Cl- -H(Me) interactions are observed in the crystals. Vibrational and electronic spectra are in agreement with the structures, illustrating p→d charge transfer interactions between the sulfide or chloride donors and the d0 or d6 metal acceptor centers, respectively. Oxidation and reduction of the compounds occur completely irreversibly.