Abstract
Hydroalumination of aryldialkynylphosphines RP(CC-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 Al 2C2P2 heterocycle with intermolecular Al-P interactions. The boat conformation (4) was obtained by the reaction of tBu-P(CC-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 CO adduct and subsequent rearrangement to the AlPC2N heterocycle, being the CN adduct.
Original language | English |
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Pages (from-to) | 9033-9045 |
Number of pages | 13 |
Journal | Dalton Transactions |
Volume | 41 |
Issue number | 30 |
DOIs | |
Publication status | Published - 14 Aug 2012 |
Externally published | Yes |
ASJC Scopus subject areas
- Inorganic Chemistry