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Abstract Addition of CO to a tetrametallic magnesium hydride cluster results in both carbon‐carbon bond formation and deoxygenation to generate an acetaldehyde enolate C 2 OH 3 − 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 C 2 OH 3 − 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 C 2 O 2 H 3 3− fragment, which undergoes subsequent deoxygenation.
Yang et al. (Tue,) studied this question.