Affiliation:
1. Inorganic Chemistry Laboratory Department of Chemistry University of Oxford South Parks Road Oxford OX1 3QR UK
2. Department of Chemistry University of Helsinki A. I. Virtasen Aukio 1, PO Box 55 00014 Helsinki Finland
Abstract
AbstractThe 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. N2O reacts rapidly to generate the organoazide DippN3(Dipp=2,6‐iPr2C6H3), 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′)−(O2C)2N‐(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, Kn[(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 CO2allows 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.
Subject
General Chemistry,Catalysis,Organic Chemistry
Cited by
3 articles.
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