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Heteroscorpionate aluminium complexes as chiral building blocks to engineer helical architectures

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Author(s)

  • Jose A Castro-Osma
  • Carlos Alonso-Moreno
  • M Victoria Gómez
  • Isabel Márquez-Segovia
  • Antonio Otero
  • Agustín Lara-Sánchez
  • Juan Fernández-Baeza
  • Luis F Sánchez-Barba
  • Ana M Rodríguez

Department/unit(s)

Publication details

JournalDalton Transactions
DateE-pub ahead of print - 1 Aug 2013
DatePublished (current) - 21 Oct 2013
Issue number39
Volume42
Number of pages13
Pages (from-to)14240-14252
Early online date1/08/13
Original languageEnglish

Abstract

Treatment of heteroscorpionate ligand precursors pbptamH, pbpamH, sbpamH and (S)-mbpamH with 2 equivalents of AlR3 (R = Et, Me) yielded the corresponding binuclear organoaluminium complexes [Al2R4(μ-pbptam)] (R = Me 1, Et 2), [Al2R4(μ-pbpam)] (R = Me 3, Et 4), [Al2R4(μ-sbpam)] (R = Me 5, Et 6) and [Al2R4{μ-(S)-mbpam}] (R = Me 7, Et 8). These complexes have helical chirality due to the demands of the fixed pyrazole rings. The stereoisomerism and the self-assembly processes of these helicates have been studied in some detail in solution by NMR and in the solid state by X-ray diffraction. Mixtures of M- and P-handed enantiomers and mixtures of M- and P-handed diastereoisomers were obtained when achiral (1–4) and chiral (5–8) heteroscorpionate ligands were used as scaffolds, respectively. Re-crystallization from hexane allowed us to obtain M-homochiral architectures in the solid state for the helical complexes [Al2Et4(μ-sbpam)] (6) and [Al2Et4{μ-(S)-mbpam}] (8). The reaction of heteroscorpionate ligands with 3 equivalents of AlR3 (R = Me, Et) led to the corresponding trinuclear organoaluminium complexes [Al3R7(μ3-pbptam)] (R = Me 9, Et 10), [Al3R7(μ3-pbpam)] (R = Me 11, Et 12), [Al3R7(μ3-sbpam)] (R = Me 13, Et 14) and [Al3R7{μ3-(S)-mbpam}] (R = Me 15, Et 16). The extra AlR3 molecule contributes to the formation of a diastereomeric excess of the PS helicate for complexes 15 and 16. X-ray determination of some of the helical complexes allowed us to witness a versatile and efficient self-assembly process of the building blocks (heteroscorpionate aluminium complexes) directed by noncovalent intermolecular CH–π interactions. The structures of these complexes have been determined by spectroscopic methods and the X-ray crystal structures of 2, 6, 8, and 16 have also been established. Concentration-dependent 1H pulsed field-gradient spin echo (PFGSE) NMR experiments provided evidence for the self-assembly of the single molecular species of complex 2 in solution. The degree of aggregation was calculated for complex 2, with the average number of units constituting the aggregate (N) estimated to be a maximum of 4 molecules in solution before reaching the solid state.

    Research areas

  • Aluminum, Coordination Complexes, Crystallography, X-Ray, Ligands, Magnetic Resonance Spectroscopy, Molecular Conformation, Stereoisomerism

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