Liu Gaoxiang, Ariyarathna Isuru R, Ciborowski Sandra M, Zhu Zhaoguo, Miliordos Evangelos, Bowen Kit H
Department of Chemistry, Johns Hopkins University, 3400 N Charles St, Baltimore, Maryland 21218,United States.
Department of Chemistry and Biochemistry, Auburn University, Auburn, Alabama 36849, United States.
J Am Chem Soc. 2020 Dec 23;142(51):21556-21561. doi: 10.1021/jacs.0c11112. Epub 2020 Dec 13.
Mass spectrometric analysis of the anionic products of interaction among Pt, methane, and carbon dioxide shows that the methane activation complex, HC-Pt-H, reacts with CO to form [HC-Pt-H(CO)]. Two hydrogenation and one C-C bond coupling products are identified as isomers of [HC-Pt-H(CO)] by a synergy between anion photoelectron spectroscopy and quantum chemical calculations. Mechanistic study reveals that both CH and CO are activated by the anionic Pt atom and that the successive depletion of the negative charge on Pt drives the CO insertion into the Pt-H and Pt-C bonds of HC-Pt-H. This study represents the first example of the simultaneous functionalization of CH and CO mediated by single atomic anions.
对铂、甲烷和二氧化碳相互作用的阴离子产物进行质谱分析表明，甲烷活化络合物HC-Pt-H与CO反应生成[HC-Pt-H(CO)]。通过阴离子光电子能谱和量子化学计算的协同作用，确定了两种氢化产物和一种C-C键偶联产物为[HC-Pt-H(CO)]的异构体。机理研究表明，CH和CO均由阴离子铂原子活化，并且铂上负电荷的连续消耗促使CO插入HC-Pt-H的Pt-H键和Pt-C键中。本研究代表了由单原子阴离子介导的CH和CO同时官能化的首个实例。
