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The reactions of tetrathiorhenate(VII) or tetrathiotungstate(VI) with [MCl 2 (C 5 Me 5 )] 2 , M = Rh or Ir, yield the neutral title compounds of which (ReS 4 )[RhCl(C 5 Me 5 )] and (μ- WS 4 )[IrCl(C 5 Me 5 )] 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 d 0  or d 6  metal acceptor centers, respectively. Oxidation and reduction of the compounds occur completely irreversibly.

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Zwei- und dreikemige Organometallkomplexe (ReS 4 )[MCl(C 5 Me 5 )], M = Rh, Ir, und (μ-WS 4 )[IrCl(C 5 Me 5 )] 2  / Dinuclear and Trinuclear Organometallic Complexes (ReS 4 )[MCl(C 5 Me 5 )], M = Rh, Ir, and (μ-WS 4 )[IrCl(C 5 Me  5)] 2