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• W2019441440 abstract "SRuCo2(CO)9 (2) entsteht in guter Ausbeute beim Erhitzen stöchiometrischer Mengen von Co2(CO)8 und Ru3(CO)12 in Gegenwart von Ethylmercaptan unter Synthesegas-Druck. In 2 lassen sich bis zu drei CO-Liganden durch PMe2Ph und bis zu zwei CO-Liganden durch AsMe2MCp(CO)3 (M = Cr, Mo, W) leicht ersetzen. Die Monosubstitutionsderivate SRuCO2(CO)8L mit L = PMe2Ph (3) bzw. L = AsMe2MCp(CO)3 (6 – 8) treten in Form von zwei Isomeren auf, bei denen wir für das zuerst gebildete Substitution am Ruthenium und anschließend Wanderung des Liganden zum Cobalt annehmen. Die Vierkernkomplexe SRuCo2(CO)8 – AsMe2MCp(CO)3 (6 – 8) unterliegen beim Erhitzen unter CO einem Metallaustausch zu den chiralen Clustern SRuCoMCp(CO)8 (12 – 14, M = Cr, Mo, W). Von diesen sind die Mo- und W- Verbindungen besser durch Umsetzung von 2 mit [MCp(CO)3]2 zugänglich. Aus SRuCoMoCp(CO)8 (13) und optisch aktiven Phosphanliganden entstehen Diastereomerengemische SRuCoMoCp(CO)7L (18: L = (–)PMePrPh; 19: L = PPh2O(–)-Menthyl). Bei der Bildung von 19 tritt eine geringe Anreicherung des (–)-Diasteromeren ein. Die Diasteromeren sind chromatographisch zu trennen, jedoch bisher nicht in die reinen Enantiomeren 13 zurückzuverwandeln. Preparation and Chemistry of the Cluster SRuCo2(CO)9 SRuCo2(CO)9 (2) results in good yield by heating of stoichiometric amounts of Co2(CO)8 and Ru3(CO)12 in the presence of ethyl mercaptan under synthesis gas pressure. In 2 up to three CO ligands can easily be replaced by PMe2Ph and up to two CO ligands by AsMe2MCp(CO)3 (M = Cr, Mo, W). The monosubstituted derivates SRuCo2(CO)8L with L = PMe2Ph (3) or L = AsMe2MCp(CO)3 (6 – 8) appear as two isomers, of which we assume substitution at ruthenium for the one formed first and subsequent transfer of the ligand to cobalt. The tetranuclear complexes SRuCo2(CO)8 – AsMe2MCp(CO)3 (6 – 8) undergo metal exchange upon heating under CO to yield the chiral clusters SRuCoMCp(CO)8 (12 – 14, M = Cr, Mo, W). Of these the Mo and W compounds are better accessible by reaction between 2 and [MCp(CO3]2. From SruCoMoCp(CO)8 (13) and optically active phosphane ligands mixtures of diastereoisomers SRuCoMoCp(CO)7L (18: L = ( – )-PMePrPh; 19: L = PPh2O( – )-Menthyl result. During the formation of 19 a slight enrichment of the ( – )-diastereoisomer occurs. The diastereoisomers can be separated chromatographically, but not yet reconverted to the pure enantiomers 13." @default.
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• W2019441440 date "1984-03-01" @default.
• W2019441440 modified "2023-09-23" @default.
• W2019441440 title "Darstellung und Chemie des Clusters SRuCo ₂ (CO) ₉" @default.
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• W2019441440 doi "https://doi.org/10.1002/cber.19841170318" @default.
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