The active Al/N Lewis pair, (Me C) Al-C(SiMe )=C(H)-N(CHMe-CH ) CH (2), reacted with isocyanates to afford a fascinating variety of products. One equivalent of Ph-N=C=O yielded by the release of H-C≡C-SiMe an urea-type ligand which coordinated the Al atom in a chelating manner (4). Dipp-N=C=O gave a similar product, but the bulky substituent hindered the approach of the N-aryl group to Al. A situation similar to that of frustrated Lewis pairs resulted in the coordination of the alkyne to the Al and N atoms (6) by C-H bond activation. Dual insertion was observed upon treatment of 2 with two equivalents of isocyanates (8 to 11). The preferred formation of cyclic oligomers is prevented by the specific cooperative properties of the Lewis pair. A metal-free dimeric isocyanate (13) was formed by hydrolysis. Replacement of the CMe groups in 2 by less bulky isobutyl groups (7) afforded the insertion of two isocyanate molecules into the Al-vinyl bonds without alkyne elimination. The resulting highly functionalised compound had a chain formed by two isocyanates and the organic backbone of the Lewis pair. Me C-N=C=O and 2 afforded a unique compound (14) in which an isocyanate ligand connects two molecules of 2 by the release of dimethylpiperidine. The combination of a C building block and two C groups gave an unsaturated branched C moiety by the simultaneous formation of two C-C bonds. The molecular structure showed an interaction between an Al atom and a C-C π-bond.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.