Influence of Coordination to Silver(I) Centers on the Activity of Heterocyclic Iodonium Salts Serving as Halogen‐Bond‐Donating Catalysts

AbstractKinetic data based on 1H NMR monitoring and computational studies indicate that in solution, pyrazole‐containing iodonium triflates and silver(I) triflate bind to each other, and such an interplay results in the decrease of the total catalytic activity of the mixture of these Lewis acids compared to the separate catalysis of the Schiff condensation, the imine–isocyanide coupling, or the nucleophilic attack on a triple carbon−carbon bond. Moreover, the kinetic data indicate that such a cooperation with the silver(I) triflate results in prevention of decomposition of the iodonium salts during the reaction progress. XRD study confirms that the pyrazole‐containing iodonium triflate coordinates to the silver(I) center via the pyrazole N atom to produce a rare example of a pentacoordinated trigonal bipyramidal dinuclear silver(I) complex featuring cationic ligands.