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

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 car...

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Bibliographic Details
Published in:Organometallics 2013-11, Vol.32 (22), p.6764-6769
Main Authors: Bertini, Federica, Hoffmann, Frank, Appelt, Christian, Uhl, Werner, Ehlers, Andreas W, Slootweg, J. Chris, Lammertsma, Koop
Format: Article
Language:English
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Summary: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.
ISSN:0276-7333
1520-6041
DOI:10.1021/om3011382