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Biphenyl-tricarbonylchrom-komplexe, 9. Mitt.: Synthesen,chromatographische Enantiomerentrennung,Circulardichroismus und Chiralität von mono- und bis-(Tricarbonylchrom)-Komplexen di- und tetrasubstituierter sowie überbrückter Biphenyle
Authors:Michael Eyer  Karl Schlögl  Michael Widhalm
Affiliation:(1) Institut für Organische Chemie, Universität Wien, A-1090 Wien, Österreich
Abstract:Chiral title compounds have been resolved by medium pressure liquid chromatography (MPLC) on triacetylcellulose in ethanol. Whereas a quantitative separation was achieved for16 and20, a recycling technique had to be applied to1,4,6,10 and15 leading to a 100% e.e. for1,6 and15 and to ca. 60% e.e. for4 and10.An unambiguous assignment of the chirality (+)-(R)a -(S)m for tricarbonylchromium-6,6prime-dimethyl-diphenicacid dimethylester (4) was deduced both from the photochemical decomplexation to (-)-5 with the known chirality (R)a (whose e.e. was determined by MPLC on triacetylcellulose) and by comparison of the1H-n.m.r. spectra of4 and5 thereby proving the structure 4 for the former.Other chiralities both for mono and bis(tricarbonylchromium)biphenyl complexes were established by chemical correlations and comparison of the CD spectra with those of key compounds.
Herrn Prof. Dr.H. Tuppy mit besten Wünschen zum 60. Geburtstag gewidmet.
Keywords:Triacetylcellulose  Recycling technique  Enantiomeric purity  Metallocene chirality  Axial chirality  Conformation
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