Consecutive C-C Coupling of CH 4 and CO 2 Mediated by Heteronuclear Metal Cations CuTa

• Published in: Journal of the American Chemical Society 2024-12
• Main Authors: Yang, Yuan, Zhang, Li-Jiao, Wang, Xiao-Li, Wang, Rui, Zhao, Yan-Xia, He, Sheng-Gui, Zang, Shuang-Quan
• Format: Article
• Language: English
• ISSN: 1520-5126

The conversion of methane and carbon dioxide to form C products is of great interest but presents a long-standing grand challenge due to the significant obstacle of activating the inert C-H and C═O bonds as well as forming the C-C bonds. Herein, the consecutive C-C coupling of CH and CO was realized by using heteronuclear metal cations CuTa , and the desorption of H C═C═O molecules was evidenced by state-of-the-art mass spectrometry. The CuTa reaction system is significantly different from the homonuclear metal systems of Cu and Ta . On the basis of density functional theory calculations, we identified that Cu can modulate the charge distribution and reduce the energy difference of crucial orbitals for the C-C coupling of CH and CO units that are from the activation of CH and CO , respectively. The crucial role of the Cu atom is of substantial importance to understand the process of the C-C coupling reaction in Cu-based heterogeneous catalytic systems. This study not only provides a promising paradigm for the design of non-noble metal species in direct conversion of CH and CO under mild conditions but also reveals a new molecular-level mechanism of consecutive C-C coupling for the production of H C═C═O, a crucial intermediate during carbonylation reactions.