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Efficient Asymmetric Synthesis of Δ‐ and Λ‐Enantiomers of (Bipyridyl)ruthenium Complexes and Crystallographic Analysis of Δ‐Bis(2,2′‐bipyridine)(2,2′‐bipyridine‐4,4′‐dicarboxylato)ruthenium: Diastereoselective Homo‐ and Heterochiral Ion Pairing Revisited
Author(s) -
Caspar Régis,
Amouri Hani,
Gruselle Michel,
Cordier Christine,
Malézieux Bernard,
Duval Raphäel,
Leveque Hubert
Publication year - 2003
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200390071
Subject(s) - chemistry , ruthenium , bipyridine , enantiomer , 2,2' bipyridine , carboxylate , circular dichroism , absolute configuration , stereochemistry , crystallography , dicarboxylic acid , chirality (physics) , crystal structure , polymer chemistry , organic chemistry , catalysis , chiral symmetry , nambu–jona lasinio model , physics , quantum mechanics , quark
Optically pure ruthenium complexes of the type Δ‐ or Λ‐[Ru(bpy) 2 (L−L)][PF 6 ] 2 [L−L = cmbpy = 4′‐methyl‐2,2′‐bipyridine‐4‐carboxylic acid ( 3a , b ); L−L = dcbpy = 2,2′‐bipyridine‐4,4′‐dicarboxylic acid ( 4a , b )] were prepared and fully characterized. The Ru II carboxylate complexes Δ‐ and Λ‐[Ru(bpy) 2 (dcabpy)] ( 5a , b ) (dcabpy = 2,2′‐bipyridine‐4,4′‐dicarboxylate) were resolved efficiently by chiral column chromatography and isolated in good yields. The Δ‐[Ru(bpy) 2 (dcabpy)] ( 5a ) enantiomer was crystallized and its X‐ray molecular structure determined. The enantiomeric nature and the absolute configuration of the tris(bipyridyl)ruthenium complexes were confirmed by NMR and circular dichroism studies. In addition, ion‐pairing interactions between Δ‐Trisphat (Δ‐ 1 , D 3 symmetry) and each enantiomer of the (monocarboxylic acid)Ru II complex ( 3a and 3b , C 1 symmetry) and the dicarboxylic acid complex ( 4a and 4b , C 2 symmetry) were examined by NMR spectroscopy. (© Wiley‐VCH Verlag GmbH & Co KGaA, 69451 Weinheim, Germany, 2003)