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C/C Exchange in Activation/Coupling Reaction of Acetylene and Methane Mediated by Os+: A Comparison with Ir+, Pt+, and Au.
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2020-09-04 , DOI: 10.1021/acs.jpclett.0c02068 Wei Li 1, 2 , Xiaonan Wu 3 , Zizhuang Liu 3 , Hechen Wu 3 , Di Zhang 3 , Xunlei Ding 1, 2
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2020-09-04 , DOI: 10.1021/acs.jpclett.0c02068 Wei Li 1, 2 , Xiaonan Wu 3 , Zizhuang Liu 3 , Hechen Wu 3 , Di Zhang 3 , Xunlei Ding 1, 2
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The activation and coupling reactions of methane and acetylene mediated by M+ (M = Os, Ir, Pt, and Au) have been comparatively studied at room temperature by the techniques of mass spectrometry in conjunction with theoretical calculations. Studies have shown that Os+ and Ir+ can mediate the activation/coupling reaction of CH4 and C2H2, while Pt+ and Au+ cannot, which could be explained by the number of empty valence orbitals in the metal atom. In addition, there are different competition channels for the reaction mediated by Os+ and Ir+: an expected dehydrogenation and an unexpected C/C exchange. We find that if the rare C/C exchange reaction takes place, there are symmetric carbon atoms in the reaction intermediate and the C/C exchange reaction is favored kinetically. The C/C exchange reaction must be considered, which will affect the yield of the products in the primary reaction. This study shows the molecular-level mechanisms which include the C/C exchange reaction in the activation and coupling reaction of organic compounds mediated by different metals.
中文翻译：
Os +介导的乙炔和甲烷活化/偶联反应中的C / C交换：与Ir +，Pt +和Au的比较。
在室温下，通过质谱技术结合理论计算，对由M +（M = Os，Ir，Pt和Au）介导的甲烷和乙炔的活化和偶联反应进行了比较研究。研究表明，Os +和Ir +可以介导CH 4和C 2 H 2的活化/偶联反应，而Pt +和Au +则不能，这可以用金属原子中的空价轨道数来解释。此外，由Os +和Ir +介导的反应存在不同的竞争通道：预期的脱氢和意外的C / C交换。我们发现，如果发生罕见的C / C交换反应，则在反应中间体中存在对称的碳原子，并且在动力学上有利于C / C交换反应。必须考虑C / C交换反应，这会影响初级反应中产物的收率。这项研究表明了分子水平的机制，包括在不同金属介导的有机化合物的活化和偶联反应中的碳/碳交换反应。
更新日期：2020-10-02
中文翻译：
Os +介导的乙炔和甲烷活化/偶联反应中的C / C交换：与Ir +，Pt +和Au的比较。
在室温下，通过质谱技术结合理论计算，对由M +（M = Os，Ir，Pt和Au）介导的甲烷和乙炔的活化和偶联反应进行了比较研究。研究表明，Os +和Ir +可以介导CH 4和C 2 H 2的活化/偶联反应，而Pt +和Au +则不能，这可以用金属原子中的空价轨道数来解释。此外，由Os +和Ir +介导的反应存在不同的竞争通道：预期的脱氢和意外的C / C交换。我们发现，如果发生罕见的C / C交换反应，则在反应中间体中存在对称的碳原子，并且在动力学上有利于C / C交换反应。必须考虑C / C交换反应，这会影响初级反应中产物的收率。这项研究表明了分子水平的机制，包括在不同金属介导的有机化合物的活化和偶联反应中的碳/碳交换反应。
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