Pairwise Assembly of Organopalladium(II) Units with Cyanurato(3−) and Trithiocyanurato(3−) Ligands: Formation of Chiral Pd(12), Pd(10), and Pd(9) Cage-Molecules

[Image: see text] The o-palladated, chloro-bridged dimers [Pd{2-phenylpyridine(-H)}-μ-Cl](2) and [Pd{N,N-dimethylbenzylamine(-H)}-μ-Cl](2) react with cyanuric acid in the presence of base to afford closed, chiral cage-molecules in which 12 organo-Pd(II) centers, located in pairs at the vertices of an octahedron, are linked by four tetrahedrally arranged cyanurato(3−) ligands. Incomplete (Pd(10)) cages, having structures derived from the corresponding Pd(12) cages by replacing one pair of organopalladium centers with two protons, have also been isolated. Reaction of [Pd{2-phenylpyridine(-H)}-μ-Cl](2) with trithiocyanuric acid gives an entirely different and more open type of cage-complex, comprising only nine organopalladium centers and three thiocyanurato(3−) ligands: cage-closure in this latter system appears to be inhibited by steric crowding of the thiocarbonyl groups.