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  • 1
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Linked chiral bipyridines 2-4 are prepared by combining two optically active ‘pineno’-[4,5]-fused 2,2′-bipyridines in a stereoselective reaction (Scheme 1). These potential ligands are new members of the ‘chiragen’ family, and are characterized by NMR spectroscopy and, in the case of 2 and 3 by single-crystal X-ray analysis. A new synthesis of ‘dipineno’-[4,5;4′,5′]-fused 2,2′ -bipyridine 8 is described, which, when coupled, gives additional four chiral centres to the analogous ‘chiragen’ series ( → 9). Analysis of the CD spectra allowed conformational information about the solution species to be determined.
    Additional Material: 6 Ill.
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  • 2
    ISSN: 1434-1948
    Keywords: Chirality ; Ruthenium ; Chiral resolution ; Nitrogen heterocycles ; Carbonyl complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A range of chiral building blocks of the type Δ- or Λ-[Ru(pp)2(CO)2]2+ {pp = bidentate ligands bpy (2,2′-bipyridine), phen (1,10-phenanthroline) and Me2bpy (4,4′-dimethyl-2,2′-bipyridine)} have been synthesized, and their enantiomeric purity and absolute configurations determined by CD and NMR studies. Decarbonylation using trimethylamine oxide in the presence of the respective pp ligand at room temperature produced the corresponding tris(bidentate) species [Ru(pp)3]2+ with retention of configuration at the ruthenium(II) centre. A general chromatographic technique for resolution of tris-homoleptic complexes of the type [Ru(pp)3]2+ was investigated, with the absolute configurations of the resolved complexes confirmed by CD studies, and the X-ray structural analyses of Δ-(-)-[Ru(Me2bpy)3]{(-)-O,O′-dibenzoyl-L-tartrate} and Λ-(+)-[Ru(phen)3]{(+)-O,O′-di-4-toluoyl-D-tartrate}. Resolution is also reported for the analogous species containing three potential bridging ligands, [Ru(bpm)3]2+ and [Ru(HAT)3]2+ (bpm = 2,2′-bipyrimidine; HAT = 1,4,5,8,9,12-hexaazatriphenylene). The versatility of the chromatographic procedure was demonstrated by the resolution of a series of bis-heteroleptic complexes [Ru(pp)2(pp′)]2+ {pp′ = dpq (dipyrido[3,2-d:2,3′-f]quinoxaline), dpqc (dipyrido[3,2-a:2,3-d]-6,7,8,9-tetrahydrophenazine), and dppz {dipyrido[3,2-a:2,3′-d]phenazine)}.
    Additional Material: 6 Ill.
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  • 3
    ISSN: 0268-2605
    Keywords: Rhenium ; carbonyl ; terpyridyl ; tris(2-pyridyl)amine ; tris(2-pyridyl)methane ; tris(2-pyridyl)phosphine ; structure ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of [Re(CO)5Cl] with the ligands tpy (2,2′:6′,2″-terpyridine), py3N {tris(2-pyridyl)-amine}, py3CH {tris(2-pyridyl)methane}, and py3P {tris(2-pyridyl)phosphine} in toluene solution realize compounds with the general formulation [Re(ligand)(CO)3Cl] in which the tripyridyl ligands are bidentate. X-ray structural determinations of fac-[Re(typ)(CO)3Cl].H2O and fac-[Re(py3N)(CO)3Cl] confirm these assignments. [Re(tpy)(CO)3Cl].H2O (C18H13ClN3O4Re) is monoclinic, space group P21/n, with cell dimensions a = 7.432(2) Å, b = 17.016(4) Å, c = 14.466(2) Å, β = 93.51(2)°, and Z = 4; full-matrix least-squares refinement on 2435 reflections with I ≥ 2.5σ(I) converged to a final R = 0.028 and Rw = 0.029. [Re(py3N)(CO)3Cl] (C18H12ClN4O3Re) is triclinic, space group P1 with cell dimensions a = 13.761(2) Å, b = 14.636(6)Å, c = 11.110(2) Å, α = 110.70(2)°, β = 102.45(2)°, γ = 107.48(2)°, and Z = 4; full-matrix least-squares refinement on 3459 reflections with I ≥ 2.5σ(I) converged to a final R = 0.038 and Rw = 0.039. If the synthetic procedure is undertaken under irradiation by visible light, for the ligand py3N a species [Re(py3N)(CO)2Cl] (characterized by infrared spectroscopy and conductance measurements) is also formed, in which the ligand py3N is tridentate. No analogous tridentate species is formed with the ligands tpy or py3P, although there is evidence that it also forms for py3CH.
    Additional Material: 3 Ill.
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