Heilmann, AndreasVasko, PetraHicks, JamieGoicoechea, Jose M.Aldridge, Simon2025-05-312025-05-310947-6539PubMed:36602941ORCID:/0000-0001-9450-2594/work/179952397http://www.scopus.com/inward/record.url?scp=85149018589&partnerID=8YFLogxKhttps://hdl.handle.net/1885/733756122The 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.This work was supported by the Leverhulme Trust (RP‐2018‐246, studentship to AH; post‐doctoral fellowship to JH). PV would like to thank the NordCO and Academy of Finland for financial support (project numbers 314794 and 346565) and CSC – IT Center for Science, Finland, for computational resources. 2enPublisher Copyright: © 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.aluminiumcarbon dioxideimidemetallacyclemetathesis2023-04-0610.1002/chem.20230001885149018589