Dimeric aluminum-phosphorus compounds as masked frustrated Lewis pairs for small molecule activation

Hydroalumination of aryldialkynylphosphines RP(CC-^tBu) <inf>2</inf> (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 Al <inf>2</inf>C<inf>2</inf>P<inf>2</inf> heterocycle with intermolecular Al-P interactions. The boat conformation (4) was obtained by the reaction of ^tBu-P(CC-^tBu)<inf>2</inf> 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 AlPC<inf>2</inf>O 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 CO adduct and subsequent rearrangement to the AlPC<inf>2</inf>N heterocycle, being the CN adduct. © 2012 The Royal Society of Chemistry.