Liu Gaoxiang, Zhu Zhaoguo, Ciborowski Sandra M, Ariyarathna Isuru R, Miliordos Evangelos, Bowen Kit H
Department of Chemistry, Johns Hopkins University, Baltimore, MD, 21218, USA.
Department of Chemistry and Biochemistry, Auburn University, Auburn, AL, 36849, USA.
Angew Chem Int Ed Engl. 2019 Jun 3;58(23):7773-7777. doi: 10.1002/anie.201903252. Epub 2019 Apr 29.
Mass spectrometric analysis of the anionic products of interaction between platinum atomic anions, Pt , and methane, CH and CD , in a collision cell shows the preferred generation of [PtCH ] and [PtCD ] complexes and a low tendency toward dehydrogenation. [PtCH ] is shown to be H-Pt-CH by a synergy between anion photoelectron spectroscopy and quantum chemical calculations, implying the rupture of a single C-H bond. The calculated reaction pathway accounts for the observed selective activation of methane by Pt . This study presents the first example of methane activation by a single atomic anion.
在碰撞池中对铂原子阴离子Pt与甲烷（CH₄和CD₄）相互作用的阴离子产物进行质谱分析，结果表明优先生成[PtCH₃]和[PtCD₃]配合物，且脱氢倾向较低。通过阴离子光电子能谱和量子化学计算的协同作用，表明[PtCH₃]为H-Pt-CH₂，这意味着单个C-H键发生断裂。计算出的反应途径解释了观察到的Pt对甲烷的选择性活化。本研究展示了单个原子阴离子活化甲烷的首个实例。
