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

Chemistry : a European Journal
Rolf W SaalfrankF Hampel

Abstract

Enantiomerically pure, vicinal diols 1 afforded in a two-step synthesis (etherification and subsequent Claisen condensation) chiral bis-1,3-diketones H(2)L((S,S)) (3 a-c) with different substitution patterns. Reaction of these C(2)-symmetric ligands with various transition-metal acetates in the presence of alkali ions generated distinct polynuclear aggregates 4-8 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)-[Cu(4)(L((S,S)))(2)(OMe)(4)] (4 a-c) or dinuclear copper(II) helicates (P)-[Cu(2)(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)-[Pd(2)(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 H(2)L((S,S)) (3 a) allowed the isolation of enantiomerically p...Continue Reading

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Citations

Oct 22, 2008·Angewandte Chemie·Rolf W SaalfrankAndreas Scheurer
Apr 1, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Peter IllnerRudi van Eldik
Feb 9, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Andreas ScheurerPaul Müller
Sep 26, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Miguel Martínez-CalvoManuel R Bermejo
Aug 22, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Jack K CleggFraser J White
Feb 16, 2012·Inorganic Chemistry·John FieldenPaul Kögerler

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