Molecular architecture of polynuclear ruthenium bipyridyl complexes with controlled metal helicity

Fletcher, Nicholas C., Keene, F. Richard, Viebrock, Heiko, and von Zelewsky, Alex (1997) Molecular architecture of polynuclear ruthenium bipyridyl complexes with controlled metal helicity. Inorganic Chemistry, 36 (6). pp. 1113-1121.

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The synthesis of di- and trinuclear ruthenium(II) complexes is reported, where each metal center has a tris(bidentate) octahedral coordination sphere with predetermined stereochemistry. New members of the "Chiragen" ligand series, consisting of two linked chiral 4,5-pineno-2,2'-bipyridine groups, have been prepared, with small spacer units between the coordination centers (−(CH₂)(subscript n) {n = 0, 3} and −CH₂(bpy)CH₂−). X-ray structural data were obtained for the ligand Chiragen[3]. (Crystal data:  orthorhombic, space group P2₁2₁2₁, a = 12.229(1) Å, b = 12.790(1) Å, c = 20.215(1) Å, V = 3161.8(4) ų, Z = 4.) Combination of the ligands with Ru(bpy)₂Cl₂ (where bpy is 2,2'-bipyridine) led to a mixture of diastereomers, while the use of enantiomerically pure Δ- or Λ-[Ru(bpy)₂(py)₂](dibenzoyltartrate) or Δ-Ru(CG[m-xyl])Cl₂ led to almost complete stereoselectivity in the products. Circular dichroism spectra show that the complexes are composed of one helical diastereomer, with the expected absolute configuration predetermined by the chiral building block used. Additionally, ¹H-NMR spectroscopy indicates C₂ point group symmetry for the structures in solution, confirming the absence of ΔΛ diastereomers.

Item ID: 22772
Item Type: Article (Research - C1)
ISSN: 1520-510X
Keywords: polypyridine complexes; electron-transfer; stereoselective synthesis; absorption-spectra; building-blocks; luminescence; ligands; photophysics; mechanism; acceptor
Date Deposited: 10 Aug 2012 01:10
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030207 Transition Metal Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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