Catalytic Formation of Five-Membered Zirconacycloallenoids and Their Reaction with Carbon Dioxide

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• 作者：Santhosh Kumar Podiyanachari ; Georg Bender ; Constantin G. Daniliuc ; Gerald Kehr ; Gerhard Erker
• 刊名：Organometallics
• 出版年：2014
• 出版时间：July 14, 2014
• 年：2014
• 卷：33
• 期：13
• 页码：3481-3488
• 全文大小：457K
• ISSN：1520-6041

文摘

Hydrozirconation of phenylacetylene followed by a reaction with ((trimethylsilyl)ethynyl)lithium gave the respective (蟽-alkenyl)(蟽-alkynyl)zirconocene complex 6a. Its treatment with a catalytic amount of B(C₆F₅)₃ (2 mol %) at room temperature resulted in efficient 蟽-ligand coupling with the formation of the isomeric five-membered zirconacycloallenoid complex 9a. Two similar examples with different substituents R¹ (SiMe₃, ^tBu) were also investigated. All three new zirconacycloallenoids (9a鈥?b>c) were characterized by X-ray diffraction. The addition reaction of carbon dioxide to the zirconacycloallenoid complex 9c and two related examples from the literature were studied. The carbon dioxide addition products were also characterized by X-ray crystal structure analysis.