AI Article Synopsis
- The addition of CNXyl and CO to a magnesium hydride cluster leads to the stepwise reduction and cross-coupling of these compounds, resulting in a new ethene amidolate ligand.
- This ligand is noteworthy for containing a 1,2-difunctionalized carbon chain, which is similar to structures in aminoalcohols and amino acids.
- DFT calculations indicate that the reaction mechanism involves a nucleophilic attack by an azamethylene intermediate on CO, with the magnesium cluster facilitating and controlling the synthesis process.
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 [OC(H)[double bond, length as m-dash]C(H)NAr] 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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| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC11290425 | PMC |
| http://dx.doi.org/10.1039/d4sc02638a | DOI Listing |
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