Cooperativity between the Silver(I) and Iodine(III) Centers in Electrophilic Activation of Organic Substrates

Kinetic data and computational study indicate that in the solution, pyrazole-containing iodolium salts and silver(I) center bind each other, and such interplay significantly affect the total catalytic activity of mixture of these Lewis acids compared with separate catalysis of the reactions required electrophilic activation of carbonyl, imino group, or triple CC bond. Moreover, the kinetic data and 1H NMR monitoring indicate that such cooperation results in prevention of decomposition of the organocatalysts by the silver(I) center during the reaction progress. XRD study indicates that in the solid state, the iodolium triflates and silver(I) triflate associate each other to give the complex species featuring triflate-bridged iodine(III) and silver(I) centers: a rare example of square-planar silver(I) complex and pentacoordinated trigonal bipyramidal dinuclear silver(I) complex.