Reactivity of Dimeric P/Al-Based Lewis Pairs toward Carbon Dioxide and tert-Butyl Isocyanate
Organometallics2013Vol. 32(22), pp. 6764–6769
Citations Over TimeTop 10% of 2013 papers
F. Bertini, Frank Hoffmann, C. Appelt, Werner Uhl, Andreas W. Ehlers, J. Chris Slootweg, Koop Lammertsma
Abstract
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–C bond of the initial heterocycle.
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