An Aluminium Imide as a Transfer Agent for the [NR]^2- Function via Metathesis Chemistry

The reactions of a terminal aluminium imide with a range of oxygen-containing substrates have been probed with a view to developing its use as a novel main group transfer agent for the [NR]^2- fragment. We demonstrate transfer of the imide moiety to [N₂ ], [CO] and [Ph(H)C] units driven thermodynamically by Al-O bond formation. N₂ O reacts rapidly to generate the organoazide DippN₃ (Dipp=2,6-ⁱ Pr₂ C₆ H₃ ), while CO₂ (under dilute reaction conditions) yields the corresponding isocyanate, DippNCO. Mechanistic studies, using both experimental and quantum chemical techniques, identify a carbamate complex K₂ [(NON)Al-{κ² -(N,O)-N(Dipp)CO₂ }]₂ (formed via [2+2] cycloaddition) as an intermediate in the formation of DippNCO, and also in an alternative reaction leading to the generation of the amino-dicarboxylate complex K₂ [(NON)Al{κ² -(O,O')-(O₂ C)₂ N-(Dipp)}] (via the take-up of a second equivalent of CO₂ ). In the case of benzaldehyde, a similar [2+2] cycloaddition process generates the metallacyclic hemi-aminal complex, K_n [(NON)Al{κ² -(N,O)-(N(Dipp)C(Ph)(H)O}]_n . Extrusion of the imine, PhC(H)NDipp, via cyclo-reversion is disfavoured thermally, due to the high energy of the putative aluminium oxide co-product, K₂ [(NON)Al(O)]₂ . However, addition of CO₂ allows the imine to be released, driven by the formation of the thermodynamically more stable aluminium carbonate co-product, K₂ [(NON)Al(κ² -(O,O')-CO₃ )]₂ .