| Chiral Benzamidinate Ligands in Rare-Earth-Metal Coordination Chemistry. | |
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MedLine Citation:
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PMID: 23015310 Owner: NLM Status: Publisher |
Abstract/OtherAbstract:
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The treatment of the recently reported potassium salt (S)-N,N'-bis-(1-phenylethyl)benzamidinate ((S)-KPEBA) and its racemic isomer (rac-KPEBA) with anhydrous lanthanide trichlorides (Ln=Sm, Er, Yb, Lu) afforded mostly chiral complexes. The tris(amidinate) complex [{(S)-PEBA}(3) Sm], bis(amidinate) complexes [{Ln(PEBA)(2) (μ-Cl)}(2) ] (Ln=Sm, Er, Yb, Lu), and mono(amidinate) compounds [Ln(PEBA)(Cl)(2) (thf)(n) ] (Ln=Sm, Yb, Lu) were isolated and structurally characterized. As a result of steric effects, the homoleptic 3:1 complexes of the smaller lanthanide atoms Yb and Lu were not accessible. Furthermore, chiral bis(amidinate)-amido complexes [{(S)-PEBA}(2) Ln{N(SiMe(3) )(2) }] (Ln=Y, Lu) were synthesized by an amine-elimination reaction and salt metathesis. All of these chiral bis- and tris(amidinate) complexes had additional axial chirality and they all crystallized as diastereomerically pure compounds. By using rac-PEBA as a ligand, an achiral meso arrangement of the ligands was observed. The catalytic activities and enantioselectivities of [{(S)-PEBA}(2) Ln{N(SiMe(3) )(2) }] (Ln=Y, Lu) were investigated in hydroamination/cyclization reactions. A clear dependence of the rate of reaction and enantioselectivity on the ionic radius was observed, which showed higher reaction rates but poorer enantioselectivities for the yttrium compound. |
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Authors:
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Paul Benndorf; Jochen Kratsch; Larissa Hartenstein; Corinna M Preuss; Peter W Roesky |
Publication Detail:
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Type: JOURNAL ARTICLE Date: 2012-9-27 |
Journal Detail:
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Title: Chemistry (Weinheim an der Bergstrasse, Germany) Volume: - ISSN: 1521-3765 ISO Abbreviation: Chemistry Publication Date: 2012 Sep |
Date Detail:
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Created Date: 2012-9-27 Completed Date: - Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 9513783 Medline TA: Chemistry Country: - |
Other Details:
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Languages: ENG Pagination: - Citation Subset: - |
Copyright Information:
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Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
Affiliation:
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Institut für Anorganische Chemie, Karlsruher Institut für Technologie (KIT), Engesserstrasse 15, 76131 Karlsruhe (Germany), Fax: (+49) 721-608-44854. |
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