Cross-coupling of CO and an isocyanide mediated by a tetrameric magnesium hydride cluster.
Chem Sci
; 15(30): 11807-11813, 2024 Jul 31.
Article
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| MEDLINE
| ID: mdl-39092134
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.
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01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
Chem Sci
Año:
2024
Tipo del documento:
Article
Pais de publicación:
Reino Unido