Unveiling Plasmon-Induced\nSuzuki–Miyaura Reactions\non Silver Nanoparticles via Raman Spectroscopy

The Suzuki–Miyaura coupling\nreaction is an efficient organic\nmethod for synthesizing biphenyl products. However, its conventional\nreliance on toxic soluble organometallic palladium catalysts or expensive\npalladium nanoparticles, along with the need for elevated temperatures\nand prolonged reaction times, presents a significant challenge. Herein,\nwe demonstrate a palladium-free approach using plasmonic silver nanoparticles\nthat enables the Suzuki–Miyaura coupling reaction to proceed\nat room temperature under visible light. Utilizing the surface-enhanced\nRaman scattering characteristics of silver, we conducted dynamic self-monitoring\nof the reaction. Our findings reveal that this plasmon-induced Suzuki–Miyaura\ncoupling reaction fundamentally operates as a heterogeneous reaction\ninvolving coupling between radicals, distinct from conventional palladium-based\nreactions. Moreover, the cleavage of C–Cl and C–B bonds,\nfundamental prerequisite to the coupling, is driven by plasmonic hot\nelectrons and plasmon-induced reactive oxygen species, respectively.\nThese findings not only provide insights into the design and regulation\nof plasmonic catalysts but also enhance theoretical understanding\nof the Suzuki–Miyaura reaction in a broader context.