1,2,4-Triazolate (tz) complexes of rhodium(I), iridium(I), and palladium(II). Crystal structure of [Rh3(µ3-tz)(µ-Cl)Cl(η4-tfbb)(CO)4]·0.5CH2Cl2(tfbb = tetrafluorobenzobarrelene), a trinuclear complex with extended metal–metal interactions

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Abstract
New binuclear complexes of formula [M2(µ-tz)2(L2)2][tz = triazolate; M = Rh or Ir, L2= diolefin, (CO)2, or (CO)(PPh3); M = Pd, L2=η3-C3H5 or η3-C4H7] have been prepared. These binuclear complexes, having unco-ordinated N atoms from the triazolate ligands, react with [M2(µ-Cl)2(L2)2](M = Rh, Ir, or Pd) to give tetranuclear compounds of formula [Rh2M2(µ3-tz)2Cl2(L2)4]. The latter complexes can also be prepared by reacting triazole and [Rh(acac)(CO)2] with [M2(µ-Cl)2(L2)2]. The heteronuclear rhodium–gold complex [Rh2Au2(µ3-tz)2Cl2(cod)2](cod = cyclo-octa- 1,5-diene) has been synthesized. Trinuclear complexes of formula [Rh2M(µ3-tz)(µ-X)ClL2(CO)4](X = Cl or OH) have been isolated by several routes starting from the above mentioned tetra-, bi-, or mononuclear complexes. In general, these trinuclear complexes show metallic lustre and marked dichroism, suggesting metal–metal interactions which were confirmed by the X-ray determination of [Rh3(µ3-tz)(µ-Cl)Cl(tfbb)(CO)4](tfbb = tetrafluorobenzobarrelene). This complex shows a stacking arrangement of centred rhodium units with an intermetallic separation of 3.425(4)Å.

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