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- W2088476701 abstract "Bei der Umsetzung von C5H5M(CO)3Cl (M Mo, W) mit Thioamiden RCSNHR* (R* = (S)-1-Phenylethyl) in Pyridin bilden sich diastereomere quadratisch-pyramidale Dicarbonyl-(cyclopentadienyl)(thioamidato)-Komplexe 2, 3, die sich nur in der Konfiguration am Metall-atom unterscheiden. Die getrennten Diastereomeren epimerisieren in Lösung durch Konfigurationsänderung am Metallatom, deren Geschwindigkeit sich polarimetrisch und 1H-NMR-spektroskopisch messen läßt. Bei der Epimerisierung, die nach 1. Ordnung verläuft, stellen sich Gleichgewichte ein, in denen die optische Induktion des (S)-1-Phenylethyl-Restes auf die Aus-bildung der beiden Metall-Konfigurationen je nach dem Substituenten zu Diastereomerenverhältnissen von 50:50 bis 87:13 führt. Optically Active Transition Metal Complexes, XL. Optically Active Dicarbonyl(cyclopentadienyl)(thioamidato) Complexes of Molybdenum and Tungsten C5H5M(CO)3Cl (M Mo, W) react with thioamides RCSNHR* (R* = (S)-1-phenylethyl) in pyridine to form diastereoisomeric square-pyramidal dicarbonyl(cyclopentadienyl)(thio-amidato)complexes 2, 3 which differ only in the configuration at the metal atom. The separated diastereoisomers epimerize in solution by change of configuration at the metal atom, the rate of which can be measured by polarimetry and 1H n.m.r. spectroscopy. In the epimerisation reaction according to 1st order kinetics, equilibria are obtained, in which the optical induction of the (S)-1-phenylethyl group on the formation of the two metal configurations leads to diastereo-isomer ratios ranging from 50:50 to 87:13, depending on the substituents." @default.
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- W2088476701 date "1977-02-01" @default.
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- W2088476701 title "Optisch aktive Übergangsmetall‐Komplexe, XL. Optisch aktive Dicarbonyl(cyclopentadienyl)(thioamidato)‐Komplexe von Molybdän und Wolfram" @default.
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- W2088476701 doi "https://doi.org/10.1002/cber.19771100235" @default.
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