)], M = Rh, Ir, und (

(1)

Zwei- und dreikernige Organometallkomplexe (ReS

₄

)[MCl(C

₅

Me

₅

)], M = Rh, Ir, und (

-WS

₄

)[IrCl(C

₅

Me

₅

)]

₂

Dinuclear and Trinuclear Organometallic Complexes (ReS

₄

)[MCl(C

₅

Me

₅

)], M = Rh, Ir, and (

-WS

₄

)[IrCl(C

₅

Me

₅

)]

₂

Matthias Wanner

^a

, Ingo Hartenbach

^a

, Jan Fiedler

^b

, Thomas Schleid

^a

und Wolfgang Kaim

^a

aInstitut f¨ur Anorganische Chemie der Universit¨at Stuttgart, Pfaffenwaldring 55, D-70550 Stuttgart, Germany

bHeyrovsky-Institut f¨ur Physikalische Chemie, Academy of Sciences of the Czech Republic, Dolejˇskova 3, CZ-18223 Prague, Czech Republic

Sonderdruckanforderungen an Prof. Dr. W. Kaim. Fax: (+49) 711 685-4165.

E-mail: kaim@iac.uni-stuttgart.de

Z. Naturforsch.56 b,940–946 (2001); eingegangen am 29. M¨arz 2001 Iridium Compounds, Rhodium Compounds, Tetrathiometallates

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 (- WS₄)[IrCl(C₅Me₅)]₂could be crystallographically characterized. The molecules contain nearly tetrahedral M'S₄units 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 elec- tronic spectra are in agreement with the structures, illustrating p^!d charge transfer interactions between the sulfide or chloride donors and the d⁰or d⁶ metal acceptor centers, respectively.

Oxidation and reduction of the compounds occur completely irreversibly.