Yang Wenbang, White Andrew J P, Crimmin Mark R
Department of Chemistry, Imperial College London, Molecular Sciences Research Hub, Imperial College London, 82 Wood Lane, White City, London, W12 0BZ, UK.
Angew Chem Int Ed Engl. 2024 Apr 2;63(14):e202319626. doi: 10.1002/anie.202319626. Epub 2024 Feb 29.
Addition of CO to a tetrametallic magnesium hydride cluster results in both carbon-carbon bond formation and deoxygenation to generate an acetaldehyde enolate [COH] 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 [COH] 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 [COH] fragment, which undergoes subsequent deoxygenation.
向四金属氢化镁簇合物中添加一氧化碳会导致碳-碳键形成和脱氧反应，生成乙醛烯醇盐[COH]，该产物仍与簇合物配位。据我们所知，这是首例通过一氧化碳与金属氢化物反应形成含有[COH]片段的可分离配合物的实例，也是首例主族金属上一氧化碳的同系化和脱氧反应实例。密度泛函理论研究表明，该反应机理的关键步骤包括氧亚甲基对甲酰基配体的亲核进攻，生成不稳定的[COH]片段，随后该片段发生脱氧反应。
