Lewis Acid Induced 尾-Elimination from a Nickelalactone: Efforts toward Acrylate Production from CO2 and Ethylene

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• 作者：Dong Jin ; Timothy J. Schmeier ; Paul G. Williard ; Nilay Hazari ; Wesley H. Bernskoetter
• 刊名：Organometallics
• 出版年：2013
• 出版时间：April 8, 2013
• 年：2013
• 卷：32
• 期：7
• 页码：2152-2159
• 全文大小：377K
• 年卷期：v.32,no.7(April 8, 2013)
• ISSN：1520-6041

文摘

The Lewis acid tris(pentafluorophenyl)borane was found to rapidly promote ring-opening 尾-hydride elimination in a 1,1鈥?bis(diphenylphosphino)ferrocene (dppf) nickelalactone complex under ambient conditions. The thermodynamic product of nickelalactone ring-opening was characterized as (dppf)Ni(CH(CH₃)CO₂BAr^f₃), the result of 尾-hydride elimination and subsequent 2,1-insertion from a transient nickel(II) acrylate hydride intermediate. Treatment of (dppf)Ni(CH(CH₃)CO₂BAr^f₃) with a nitrogen-containing base afforded a diphosphine nickel(0) 畏²-acryl borate adduct. Formation of the diphosphine nickel(0) 畏²-acryl borate adduct completes a net conversion of nickelalactone to acrylate species, a significant obstacle to catalytic acrylate production from CO₂ and ethylene. Displacement of the 畏²-acrylate fragment from the nickel center was accomplished by addition of ethylene to yield a free acrylate salt and (dppf)Ni(CH₂鈺怌H₂).