Surface-Plasmon-Enhanced Transmetalation between Copper and Palladium Nanoparticle Catalyst

Surface-plasmon-mediated phenylacetylide intermediate transfer from the Cu to the Pd surface affords a novel mechanism for transmetalation, enabling wavelength-tunable cross-coupling and homo-coupling reaction pathway control. C-C bond forming Sonogashira coupling and Glaser coupling reactions in O-2 atmosphere are efficiently driven by visible light over heterogeneous Cu and Pd nanoparticles as a mixed catalyst without base or other additives. The reaction pathway can be controlled by switching the excitation wavelength. Shorter wavelengths (400-500 nm) give the Glaser homo-coupling diyne, whereas longer wavelength irradiation (500-940 nm) significantly increases the degree of cross-coupling Sonogashira coupling products. The ratio of the activated intermediates of alkyne to the iodobenzene is wavelength dependent and this regulates transmetalation. This wavelength-tunable reaction pathway is a novel way to optimize the product selectivity in important organic syntheses.

Automated summary

This study identifies a surface-plasmon-mediated mechanism for transmetalation, which enables efficient carbon-carbon bond formation reactions driven by visible light without the need for bases or other additives. The reaction pathway can be controlled by switching the excitation wavelength, providing a novel way to optimize product selectivity in organic syntheses.