Steering the Reaction Pathways of Terminal Alkynes by Introducing Oxygen Species: From C-C Coupling to C-H Activation

Selective regulation of chemical reactions is crucial in chemistry. Oxygen, as a key reagent in ubiquitous oxidative chemistry, exhibits great potential in regulating molecular assemblies, and more importantly, chemical reactions in molecular systems supported by metal surfaces. However, the unique catalytic performance and reaction mechanisms of oxygen species remain elusive, which are essential for understanding reaction selection and regulation. In this study, by a combination of scanning tunneling microscopy (STM) imaging/manipulations and density functional theory (DFT) calculations, we showed that the on-surface reaction pathways of terminal alkynes could be steered from C-C coupling to C-H activation with high selectivity by introducing O₂ into the molecular system. The catalytic performance and reaction mechanisms of oxygen species were explored in the C-H activation processes, and both molecular O₂ and atomic O could efficiently steer the reaction pathways. These results would provide a fundamental understanding of interfacial catalytic reaction processes.