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- W2024961104 abstract "Bei der Umsetzung von Cobalticiniumchlorid (1) mit Organyl-Verbindungen von Li, Mg, Al oder Zn entstehen, abhängig vom Metall, dem Organylrest, dem Lösungsmittel und der Reaktionstemperatur die (η5-Cyclopentadienyl)(η4-5-organyl-1,3-cyclopentadien)cobalt-Komplexe 4a–j oder Cobaltocen (2) bzw. deren Mischungen. Aus der ausschließlichen Bildung der exo-5-Organylderivate 4 wird auf einen Reaktionsverlauf über Cobalticinium-chloroorganylmetallate 3 und/oder Cobalticinium-alkanide C geschlossen. Komplexe 3 konnten mit Aluminium- und Zinkverbindungen erhalten werden. Cobalticiniumsalze des Typs C wurden bei der Umsetzung von 1 mit Natriummethylat oder -ethylat als Solvat-Komplexe 5 nachgewiesen, die beim Entfernen des Solvatalkohols in (η4-exo-5-Alkoxy-1,3-cyclopentadien)(η5-cyclopentadienyl)cobalt-Komplexe 6 übergehen. — Im Gegensatz zu den instabilen Bis(cyclopentadienyl)organylcobalt-Komplexen B, die unter Bildung von 2, zerfallen, können durch Umsetzung von (η3-Allyl)(η5-cyclopentadienyl)-cobaltbromid (7) mit Organolithium oder -magnesiumhalogeniden entsprechende Organocobalt-Komplexe 8a–f erhalten werden. 8d isomerisiert bei 20°C unter Verknüpfung von Vinyl- und Allylgruppe zu den (η4-1,3-Pentadien)cobalt-Komplexen 9a und b. (Cyclopentadienyl)organylcobalt Complexes Reaction of cobalticinium chloride (1) with organometallic compounds of Li, Mg, Al, and Zn leads (depending upon the metal, the organic group, the solvent, and the reaction temperature) to the formation of the (η5-cyclopentadienyl)(η4-5-organyl-1,3-cyclopentadiene)cobalt complexes 4a–j or cobaltocene (2) or mixtures of both. The exclusive formation of the exo-5-organyl derivatives 4 suggests a mechanism involving a cobalticinium chloroorganometallate species 3 or a cobalticinium alkanide species C. Complexes 3 were isolated from the reaction with aluminium or zinc compounds. Solvated cobalticinium salts of type C were identified in the reactions of 1 with sodium methoxide or ethoxide. They react further to (η5-cyclopentadienyl)(η4-exo-5-alkoxy-1,3-cyclopentadiene)cobalt complexes 6 upon removing the solvating alcohol. — In contrast to the unstable bis(cyclopentadienyl)organylcobalt complexes B (which react further to 2), the corresponding organylcobalt complexes 8a–f were obtained from the reaction of (η3-allyl)(η5-cyclopentadienyl)cobalt bromide 7 with organolithium or -magnesium halides. At 20°C 8d isomerizes by coupling of the vinyl and the allyl group into the (η4-1,3-pentadiene)cobalt complexes 9a and b." @default.
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- W2024961104 date "1984-12-01" @default.
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- W2024961104 title "Über (Cyclopentadienyl)organylcobalt‐Komplexe" @default.
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- W2024961104 doi "https://doi.org/10.1002/cber.19841171213" @default.
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