Journal
INORGANIC CHEMISTRY
Volume 39, Issue 2, Pages 317-324Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic991059d
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A new concept in the synthesis of optically active octahedral ruthenium complexes was realized for the first time when cis- or trans-Ru(bpy)(2)Cl, (cis- or trans-1) was reacted with either (R)-(+)- or (S)-(-)-methyl p-tolyl sulfoxide (2 or 3); this novel asymmetric synthesis leads to the diastereoselective formation of the ruthenium bis(bipyridine) complex cis-Delta-[Ru(bpy)(2)(2)Cl]Cl (4) (49.6% de) or cis-Lambda-[Ru(bpy)(2)(3)Cl]Cl (5) (48.4% de), respectively cis- or trans-Ru(dmbpy)(2)Cl-2 (cis- or trans-6) (dmbpy = 4,4'-dimethyl-2,2'-bipyridine) also reacts with 2 or 3, leading to the diastereoselective formation of cis-Delta-[Ru(dmbpy)(2)(2)Cl]Cl (7) (59.5 % de) or cis-Lambda-[Ru(dmbpy)(2)(3)Cl]Cl (8) (57.2% de), respectively. The diastereoselectivity of these reactions is governed solely by the chirality of the sulfoxide nucleophile. This represents the first process by which a a-bonded ligand occupying only a single coordination site has had such an important influence on the stereochemical outcome of a ruthenium bis(bipyridine) complex formation. These novel complexes were fully characterized by elemental analysis and IR, UV/vis, and H-1, C-13, and 2D NMR spectroscopy. An investigation into the chiroptical properties of these novel ruthenium bis(bipyridine) sulfoxide complexes has been carried out, and circular dichroism spectra are used to assign absolute stereochemistry.
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