Issue 30, 2024

Cross-coupling of CO and an isocyanide mediated by a tetrameric magnesium hydride cluster

Abstract

Sequential addition of CNXyl (Xyl = 2,6-dimethylphenyl) and CO to a tetrametallic magnesium hydride cluster results in stepwise reduction and cross-coupling of these substrates. Cross-coupling results in the formation of an ethene amidolate ligand [OC1(H1)[double bond, length as m-dash]C2(H2)NAr]2− a previously unknown entity which contains a 1,2-difunctionalised carbon chain reminiscent of those found in aminoalcohols and amino acids. To the best of our knowledge, this is the first example of such reactivity with metal hydride precursors. DFT calculations support a mechanism that parallels that established for coupling of CO to form ethenediolate ligands, with the key carbon–carbon bond step occurring by nucleophilic attack of a putative azamethylene intermediate on CO. The cluster plays a key role in templating the synthesis, providing kinetic control over each of the steps. The ethene amidolate ligand can be transferred to other metals (Al) and semi-metals (B) through onwards metathesis reactions.

Graphical abstract: Cross-coupling of CO and an isocyanide mediated by a tetrameric magnesium hydride cluster

Supplementary files

Article information

Article type
Edge Article
Submitted
21 Apr 2024
Accepted
22 Jun 2024
First published
24 Jun 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 11807-11813

Cross-coupling of CO and an isocyanide mediated by a tetrameric magnesium hydride cluster

W. Yang, A. J. P. White and M. R. Crimmin, Chem. Sci., 2024, 15, 11807 DOI: 10.1039/D4SC02638A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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