4.8 Article

Structural snapshots of an Al-Cu bond-mediated transformation of terminal acetylenes

Journal

CHEMICAL SCIENCE
Volume 14, Issue 11, Pages 2866-2876

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d3sc00240c

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The copper(i) alumanyl derivative reacts with up to three equivalents of various terminal alkynes, resulting in the sequential formation of cuprous (hydrido)(alkynyl)aluminate, (alkenyl)(alkynyl)aluminate, and bis(alkynyl)aluminate derivatives. The alkene liberation process in the latter step is a unique case of alkyne transfer semi-hydrogenation.
The copper(i) alumanyl derivative, [{SiNDipp}Al-Cu(NHCiPr)] (SiNDipp = {CH(2)SiMe(2)NDipp}(2); Dipp = 2,6-di-isopropylphenyl; NHCiPr = N,N '-di-isopropyl-4,5-dimethyl-2-ylidene), reacts in a stepwise fashion with up to three equivalents of various terminal alkynes. This reactivity results in the sequential formation of cuprous (hydrido)(alkynyl)aluminate, (alkenyl)(alkynyl)aluminate and bis(alkynyl)aluminate derivatives, examples of which have been fully characterised. The process of alkene liberation resulting from the latter reaction step constitutes a unique case of alkyne transfer semi-hydrogenation in which the C-H acidic alkyne itself acts as a source of proton, with the Cu-Al bond providing the requisite electrons to effect reduction. This reaction sequence is validated by DFT calculations, which rationalise the variable stability of the initially formed heterobimetallic hydrides.

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