Reactivity of Dimeric P/Al-Based Lewis Pairs toward Carbon Dioxide and tert-Butyl Isocyanate

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• 作者：Federica Bertini ; Frank Hoffmann ; Christian Appelt ; Werner Uhl ; Andreas W. Ehlers ; J. Chris Slootweg ; Koop Lammertsma
• 刊名：Organometallics
• 出版年：2013
• 出版时间：November 25, 2013
• 年：2013
• 卷：32
• 期：22
• 页码：6764-6769
• 全文大小：356K
• 年卷期：v.32,no.22(November 25, 2013)
• ISSN：1520-6041

文摘

The methylene-bridged phosphinoalane tBu₂PCH₂AlMe₂ exists as a stable, dimeric Lewis adduct, which reacts with carbon dioxide and tert-butyl isocyanate at room temperature, forming five-membered heterocycles; we explored the reaction pathways of these heterocycles with computational chemistry. A carboxylate dimer results when excess carbon dioxide is used. A novel mechanism is presented for this process that presumes the cooperative effect of two CO₂ molecules in which the FLP captured CO₂ is expelled on insertion of a second molecule into the Al鈥揅 bond of the initial heterocycle.