Abstract
Investigating the mechanism of a complex catalytic reaction is usually quite complicated because many processes, such as active catalyst formation and deactivation, are linked to the main catalytic cycle. Using artificial multi-route reactions with similar competing substrates is a unique way to elucidate the fine details of a reaction mechanism. Applying such multi-route reaction-based methods to the cross-coupling of alkynes with aryl halides (Cu-free Sonogashira reaction) and alkenes with aromatic carboxylic anhydrides (modified Heck reaction) catalysed by ligand-free Pd allowed us to elucidate the fast, reversible, and rate-determining steps involved in the relevant catalytic cycles.
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