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.


Supplementary material

Supporting Information
1H NMR monitoring of the Groebke–Blackburn–Bienaymé reaction; 1H NMR Monitoring of the first step of the reaction; 1H NMR monitoring of the second step of the reaction; 1H NMR monitoring of the silver(I)-catalyzed intermolecular rearrangement; 1H NMR titration data; Synthesis and characterization of С, F and H; Synthesis and characterization of Cat1OTf–Cat4OTf; Spectra of C, F, H, Cat1OTf–Cat4OTf; Table S1. Crystal data for Cat13[Ag(OTf)4] and [Ag2(Cat4)2(MeOH)2(OTf)2](OTf)2; Details of QTAIM analysis; Table S2. Cartesian atomic coordinates for model structures; Table S3. Calculated total electronic energies, enthalpies, Gibbs free energies, and entropies for optimized equilibrium model structures.
Optimized Equilibrium Structures
Results of DFT calculations in xyz format