Lewis Acid−Base Interactions between Metal Atoms and Their Applications for the Synthesis of Bimetallic Cluster Complexes

Abstract
A series of new palladium−ruthenium cluster complexes have been prepared by adding Pd(PBut3) fragments to the ruthenium−ruthenium bonds of ruthenium carbonyl complexes. Reaction of Pd(PBut3)2 with Ru3(CO)12 yielded the tripalladium adduct Ru3(CO)12[Pd(PBut3)]31. Compound 1 contains three Pd(PBut3) groups symmetrically disposed with each one acting as a bridge across one Ru−Ru bond of the former Ru3(CO)12 molecule. Reaction of Pd(PBut3)2 with Ru6(CO)17(C) yielded the dipalladium adduct Ru6(CO)17(C)[Pd(PBut3)]22. Compound 2 exists as two isomers in the solid state. One isomer has Pd(PBut3) groups bridging two edges of the Ru6 octahedron. The other isomer has a Pd(PBut3) group bridging one edge of the Ru6 octahedron, and the other is a triple bridge. The reaction of Pd(PBut3)2 with Ru(CO)5 yielded the dipalladium−diruthenium complex Ru2(CO)9[Pd(PBut3)]23, a dipalladium adduct of the unstable molecule Ru2(CO)9.

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