Department of Chemistry, Stanford University, 333 Campus Drive, Stanford, CA 94305-5080 (USA).
Angew Chem Int Ed Engl. 2014 May 26;53(22):5648-52. doi: 10.1002/anie.201400134. Epub 2014 Apr 7.
The activation of O2 is a key step in selective catalytic aerobic oxidation reactions mediated by transition metals. The bridging trinuclear palladium species, (LPd(II))3(μ(3)-O)2 (L=2,9-dimethylphenanthroline), was identified during the [LPd(OAc)]2(OTf)2-catalyzed aerobic oxidation of 1,2-propanediol. Independent synthesis, structural characterization, and catalytic studies of the trinuclear compound show that it is a product of oxygen activation by reduced palladium species and is a competent intermediate in the catalytic aerobic oxidation of alcohols. The formation and catalytic activity of the trinuclear Pd3O2 species illuminates a multinuclear pathway for aerobic oxidation reactions catalyzed by Pd complexes.
O2 的活化是过渡金属介导的选择性催化有氧氧化反应的关键步骤。在 [LPd(OAc)]2(OTf)2 催化 1,2-丙二醇的有氧氧化过程中，发现了桥联三核钯物种 (LPd(II))3(μ(3)-O)2（L=2,9-二甲基菲咯啉）。三核化合物的独立合成、结构表征和催化研究表明，它是还原钯物种氧活化的产物，也是醇催化有氧氧化的有效中间体。三核 Pd3O2 物种的形成和催化活性阐明了 Pd 配合物催化的有氧氧化反应的多核途径。
