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. 2024 Apr 2;63(14):e202319626.
doi: 10.1002/anie.202319626. Epub 2024 Feb 29.

Deoxygenative Coupling of CO with a Tetrametallic Magnesium Hydride Complex

Wenbang Yang  1 , Andrew J P White  1 , Mark R Crimmin  1
Affiliations

Deoxygenative Coupling of CO with a Tetrametallic Magnesium Hydride Complex

Wenbang Yang et al. Angew Chem Int Ed Engl. .

Abstract

Addition of CO to a tetrametallic magnesium hydride cluster results in both carbon-carbon bond formation and deoxygenation to generate an acetaldehyde enolate [C2OH3]- which remains coordinated to the cluster. To the best of our knowledge, this is the first example of formation of an isolable complex containing an [C2OH3]- fragment from reaction of CO with a metal hydride, and the first example of CO homologation and deoxygenation at a main group metal. DFT studies suggest that key steps in the mechanism involve nucleophilic attack of an oxymethylene on a formyl ligand to generate an unstable [C2O2H3]3- fragment, which undergoes subsequent deoxygenation.

Keywords: Carbon Monoxide; Deoxygenation; Homologation; Hydride; Magnesium.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Examples of CO coupling and deoxygenation with metal hydrides. Non‐hydride and CO derived ligands have been omitted for clarity.
Figure 2
Figure 2
(a) Tetrameric magnesium hydride cluster 1 and its reaction with CO. (b) The crystal structure of 2.
Figure 3
Figure 3
Reactions of 2 with Ph2CO, CNXyl (Xyl=2,6‐dimethylphenyl), PhCN, and t‐BuN=C=O. Ar=2,6‐di‐iso‐propylphenyl. Isolated yields in parentheses.
Figure 4
Figure 4
The crystal structure of 3b.
Figure 5
Figure 5
Proposed pathway for CO coupling and deoxygenation based on DFT calculations G09: ωB97X‐D/6‐311+G**/PCM (benzene)//ωB97X‐D/6‐31G**/6‐311+G*/SDDAll (Mg).
Figure 6
Figure 6
Electron‐flow in the deoxygenation step.
See this image and copyright information in PMC

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