Iridium-bismuth carbonyl cluster complexes Dedicated to the memory of Professor Jack Lewis, the Lord Lewis of Newnham, a pioneer in the chemistry of polynuclear metal carbonyl cluster complexes.

The compound Ir3(CO)9(μ3-Bi), 1 loses CO when heated and condenses to form the hexairidium compoun Ir6(CO)13(μ3-Bi)(μ4-Bi), 2. Compounds 1 and 2 react with PPh3 to form the PPh3 derivatives Ir3(CO)9-n(PPh3)n(μ3-Bi), 3 - 5, n = 1-3 and Ir6(CO)12(PPh3)(μ3-Bi)(μ4-Bi), 6, respectively. Compound 4 loses CO and converts to the o-metallated product Ir3(CO)6(PPh3)(μ-C6H4PPh2)(μ-H)(μ3-Bi), 7. Compound 1 reacts with Ru3(CO)10(NCMe)2 to yield the bimetallic cluster complex Ir3Ru4(CO)18(μ3-Bi), 9. The structures of all new products were established by single-crystal X-ray diffraction analyses. The hexairidium products 2 and 6 contain square pyramidal Ir5 clusters with a quadruply bridging bismuth ligand across the square base and a triply bridging bismuth ligand on one of the Ir3 triangles. The sixth Ir grouping is a capping group on one of the remaining Ir3 triangles. Compound 9 contains an octahedral Ir3Ru3 cluster with a Ru(CO)3 group capping an Ir3 triangle and a triply bridging bismuth ligand on one of the IrRu2 triangles. © 2015 Elsevier B.V. All rights reserved.