Cross-coupling of CO and an isocyanide mediated by a tetrameric magnesium hydride cluster
File(s)
Published version
Author(s)
Yang, Wenbang
White, Andrew JP
Crimmin, Mark R
Type
Journal Article
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.
Date Issued
2024-07-31
Date Acceptance
2024-06-22
Citation
Chemical Science, 2024, 15 (30), pp.11807-11813
ISSN
2041-6520
Publisher
The Royal Society of Chemistry
Start Page
11807
End Page
11813
Journal / Book Title
Chemical Science
Volume
15
Issue
30
Copyright Statement
© 2024 The Author(s). Published by the Royal Society of Chemistry Open Access Article. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
License URL
Identifier
https://www.ncbi.nlm.nih.gov/pubmed/39092134
PII: d4sc02638a
Subjects
ALKYL
BUTYL ISOCYANIDE
CARBON-MONOXIDE ACTIVATION
Chemistry
Chemistry, Multidisciplinary
COMPLEXES
DERIVATIVES
DOUBLE INSERTION
HOMOLOGATION
HYDROGENATION
METHYL ISOCYANIDE
ORGANOACTINIDES
Physical Sciences
Science & Technology
Publication Status
Published
Coverage Spatial
England
Article Number
11807
Date Publish Online
2024-06-24