Click Chemistry: Copper Clusters Catalyse the Cycloaddition of Azides with Terminal Alkynes
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Sonogashira K., 1997, Metal‐Catalyzed Cross Coupling Reactions
Another factor that may play a role in the efficiency of heterogeneous copper catalysts is that the surface of copper metal is usually coated by a monolayer of Cu(I) oxide a dark red powder when in bulk but virtually unnoticeable when on the metal which may serve as the source of Cu(I). This may explain why the reaction slows down and eventually stops but does not stop immediately after copper metal is removed.
Kurumi M., 2000, Heterocycles, 12, 2809