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- W1991018047 abstract "Die Ether-Phosphan-Liganden R2P↷D (2a–d) reagieren mit RuCl3·3H2O (1) zu den Komplexen Cl2Ru(R2P↷D)2 (3a–d), in denen die P,O-Liganden 2a–d zweizähnig fungieren. Mit CO wird eine Ru–O-Bindung geöffnet unter Bildung von trans-Cl2-(R2P↷D)(R2P↷D)RuCO (4a–d). Bei der Einführung eines zweiten CO-Moleküls in 4a, b läßt sich auch die andere RuO-Bindung spalten. Die kinetisch gelenkt entstehenden Produkte all-trans-RuCl2(CO)2(R2P∼D)2 (all-trans-5a, b) wandeln sich beim Erwärmen in die thermodynamisch stabileren Komplexe cis-Cl2(OC)2Ru(trans-R2P∼D)2 (cis,cis,trans-5a, b) um. Alle Reaktionschritte sind reversibel. Beim Bestrahlen wandeln sich cis,cis,trans-5a, b über all-trans-5a, b und 4a, b in 3a, b zurück. Der Auf- und Zuklappmechanismus der P, O-Liganden 2a, b kann IR- und 31P{1H}-NMR-spektroskopisch verfolgt werden. Nach Röntgenstrukturanalysen kristallisieren 3b und 4b in der monoklinen bzw. triklinen Raumgruppe P21/n bzw. P1 mit Z = 4 bzw. 2. 4b katalysiert die Hydrierung von Acetaldehyd zu Ethanol. Novel Basic Ligands for the Homogeneous Catalytic Methanol Carbonylation, IX1). –Synthesis and Reactivity of Ruthenium(II) Complexes with Ether Phosphane Ligands The ether phosphane ligands R2P↷D (2a–d) react with RuCl3·3H2O (1) to give the complexes Cl2Ru(R2P↷D)2 (3a–d) in which the P,O ligands 2a–d function as bidentates. With CO one Ru–O bond is ruptured with formation of trans-Cl2-(R2P∼D)(R2P↷D)RuCO (4a–d). Upon introduction of a second CO molecule in 4a, b, also the other Ru–O bond is cleaved. On heating the kinetically controlled products all-trans-RuCl2(CO)2(R2P∼D)2 (all-trans-5a, b) are transformed into the thermodynamically more stable complexes cis-Cl2(OC)2Ru(trans-R2P˜D)2 (cis,cis,trans-5a, b). All reaction steps are reversible. Upon irradiation cis,cis,trans-5a, b are retransformed into 3a, b via all-trans-5a, b and 4a, b. The opening and closing mechanism of the P,O ligands 2a, b is observed by IR and 31P{1H} NMR spectroscopy. According to X-ray structural analyses, 3b and 4b crystallize in the monoclinic and triclinic space group P21/n and P1 with Z = 4 and 2, respectively. 4b catalyses the hydrogenation of acetaldehyde to ethanol." @default.
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- W1991018047 date "1987-10-01" @default.
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- W1991018047 title "Neuartige basische Liganden für die homogenkatalytische Methanolcarbonylierung, IX <sup>1)</sup> Synthese und Reaktivität von Ruthenium(II)‐Komplexen mit Ether‐Phosphan‐Liganden" @default.
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- W1991018047 doi "https://doi.org/10.1002/cber.19871201005" @default.
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