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Enantiospecific Syntheses of Copper Cubanes, Double-Stranded Copper/Palladium Helicates, and a (Dilithium)–Dinickel Coronate from Enantiomerically Pure Bis-1,3-diketones—Solid-State Self-Organization Towards Wirelike Copper/Palladium Strands


  • Chelate Complexes, Part 38; for Part 37, see reference 26g.


Enantiomerically pure, vicinal diols 1 afforded in a two-step synthesis (etherification and subsequent Claisen condensation) chiral bis-1,3-diketones H2L(S,S) (3 ac) with different substitution patterns. Reaction of these C2-symmetric ligands with various transition-metal acetates in the presence of alkali ions generated distinct polynuclear aggregates 48 by diastereoselective self-assembly. Starting from copper(II) acetate monohydrate and depending on the ratio of transition-metal ion to alkali ion to ligand, chiral tetranuclear copper(II) cubanes (C,C,C,C)-[Cu4(L(S,S))2(OMe)4] (4 ac) or dinuclear copper(II) helicates (P)-[Cu2(L(S,S))2] (5) could be synthesized with square-pyramidal and square-planar coordination geometry at the metal center. In analogy to the last case, with palladium(II) acetate double-stranded helical systems (P)-[Pd2(L(S,S))2] (6,7) were accessible exhibiting a linear self-organization of ligand-isolated palladium filaments in the solid state with short inter- and intramolecular metal distances. Finally, the introduction of hexacoordinate nickel(II) in combination with lithium hydroxide monohydrate and chiral ligand H2L(S,S) (3 a) allowed the isolation of enantiomerically pure dinuclear nickel(II) coronate [(Li⋅MeOH)2⊂{(Δ,Λ)-Ni2(L(S,S))2(OMe)2}] (8) with two lithium ions in the voids, defined by the oxygen donors in the ligand backbone. The high diastereoselectivity, induced by the chiral ligands, during the self-assembly process in the systems 48 could be exemplarily proven by circular dichroism spectroscopy for the synthesized enantiomers of the chiral copper(II) cubane 4 a and palladium(II) helicate 6.