Reaction of Zirconocene鈥揅arboryne with Alkenes: Synthesis and Structure of Zirconacyclopentanes with a Carborane Auxiliary

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• 作者：Shikuo Ren ; Zaozao Qiu ; Zuowei Xie
• 刊名：Organometallics
• 出版年：2012
• 出版时间：June 25, 2012
• 年：2012
• 卷：31
• 期：12
• 页码：4435-4441
• 全文大小：439K
• 年卷期：v.31,no.12(June 25, 2012)
• ISSN：1520-6041

文摘

Reaction of zirconocene鈥揷arboryne in situ generated from Cp₂Zr(渭-Cl)(渭-C₂B₁₀H₁₀)Li(OEt₂)₂ with various alkenes RCH鈺怌H₂ in refluxing toluene gave the monoinsertion products 1,2-[Cp₂ZrCH(R)CH₂]-1,2-C₂B₁₀H₁₀ (R = aryl) or 1,2-[Cp₂ZrCH₂CH(R)]-1,2-C₂B₁₀H₁₀ (R = alkyl) in good to high isolated yields with very high regioselectivity, depending on the polarity of the alkenes. This reaction offered an efficient route to zirconacyclopentanes with a carborane auxiliary, which can be viewed as a carborane version of zirconacyclopentanes. They are thermally very stable and chemically inert toward unsaturated organic molecules such as alkenes, alkynes, nitriles, CO, and CO₂. All complexes have been fully characterized by various spectroscopic techniques. Some have been further confirmed by single-crystal X-ray analyses.