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Issue 30, 2012
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Dimeric aluminum–phosphorus compounds as masked frustrated Lewis pairs for small molecule activation

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Abstract

Hydroalumination of aryldialkynylphosphines RP(C[triple bond, length as m-dash]C–tBu)2 (R = Ph, Mes) with equimolar quantities of diethylaluminum hydride afforded mixed alkenyl–alkynyl cyclic dimers in which the dative aluminum–phosphorus bonds are geminal to the exocyclic alkenyl groups. Addition of triethylaluminum to isolated 1 (R = Ph) or to the in situ generated species (R = Mes) caused diethylaluminum ethynide elimination to yield the arylethylphosphorus dimers 2 and 3. These possess a chair-like Al2C2P2 heterocycle with intermolecular Al–P interactions. The boat conformation (4) was obtained by the reaction of tBu–P(C[triple bond, length as m-dash]C–tBu)2 with di(tert-butyl)aluminum hydride. Despite being dimeric, 2 behaves as a frustrated Lewis pair and activates small molecules. The reaction with carbon dioxide gave cis/trans isomeric AlPC2O heterocycles that differ only by the configuration of the exocyclic alkenyl unit. Four isomers resulted from the reaction with phenyl isocyanate. This is caused by cis/trans isomerization of the initial C[double bond, length as m-dash]O adduct and subsequent rearrangement to the AlPC2N heterocycle, being the C[double bond, length as m-dash]N adduct.

Graphical abstract: Dimeric aluminum–phosphorus compounds as masked frustrated Lewis pairs for small molecule activation

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Publication details

The article was received on 12 Jan 2012, accepted on 13 Feb 2012 and first published on 15 Feb 2012


Article type: Paper
DOI: 10.1039/C2DT30080J
Citation: Dalton Trans., 2012,41, 9033-9045
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    Dimeric aluminum–phosphorus compounds as masked frustrated Lewis pairs for small molecule activation

    S. Roters, C. Appelt, H. Westenberg, A. Hepp, J. C. Slootweg, K. Lammertsma and W. Uhl, Dalton Trans., 2012, 41, 9033
    DOI: 10.1039/C2DT30080J

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