Document Detail

Chiral Benzamidinate Ligands in Rare-Earth-Metal Coordination Chemistry.
MedLine Citation:
PMID:  23015310     Owner:  NLM     Status:  Publisher    
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.
Paul Benndorf; Jochen Kratsch; Larissa Hartenstein; Corinna M Preuss; Peter W Roesky
Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-9-27
Journal Detail:
Title:  Chemistry (Weinheim an der Bergstrasse, Germany)     Volume:  -     ISSN:  1521-3765     ISO Abbreviation:  Chemistry     Publication Date:  2012 Sep 
Date Detail:
Created Date:  2012-9-27     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9513783     Medline TA:  Chemistry     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Copyright Information:
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Institut für Anorganische Chemie, Karlsruher Institut für Technologie (KIT), Engesserstrasse 15, 76131 Karlsruhe (Germany), Fax: (+49) 721-608-44854.
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