An aluminium imide as a transfer agent for the [NR]2- function via metathesis chemistry

DOI: 10.1002/chem.202300018

Authors: Andreas Heilmann (University of Oxford) , Petra Vasko (University of Helsinki) , Jamie Hicks (University of Oxford) , Jose M. Goicoechea (University of Oxford) , Simon Aldridge (University of Oxford)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemistry – A European Journal

State: Published (Approved)
Published: January 2023

Abstract: 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. 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 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.

Journal Keywords: aluminium; imide; carbon dioxide; metathesis; metallacycle

Subject Areas: Chemistry


Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 09/01/2023 08:43

Discipline Tags:

Molecular Complexes Physical Chemistry Catalysis Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)