✍ Scribed by Anny Jutand
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Chloride ions play a very important role in palladium‐catalyzed reactions. This review illustrates how chloride ions modify: (i) the kinetics of the oxidative addition of aryl triflates, vinyl triflates, allylic acetates to palladium(0) complexes; (ii) the structure of the aryl‐, vinyl‐ or allyl‐palladium(II) complexes, generated in the oxidative addition, by formation of neutral aryl‐, vinyl‐ or η^1^‐allyl‐palladium(II) chloride complexes respectively, instead of cationic aryl‐, vinyl‐ or (η^3^‐allyl)palladium(II) complexes; (iii) the mechanism of the second step of the catalytic cycle of the Stille reactions of aryl or vinyl triflates by formation of neutral aryl‐ or vinyl‐ chloride complexes able to react with the nucleophile; and (iv) the mechanism of the second step of the catalytic cycle of the Tsuji–Trost reactions, i.e. the nucleophilic attack on allyl‐palladium(II) complexes (neutral η^1^‐allyl‐PdCl versus cationic (η^3^‐allyl)palladium(II) complexes). Copyright © 2004 John Wiley & Sons, Ltd.
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