RESUMO
Sulfonium, selenonium, telluronium, and iodonium cyanoborohydrides have been synthesized, isolated, and fully characterized by various methods, including single-crystal X-ray diffraction (XRD) analysis. The quantum theory of atoms in molecules' analysis based on the XRD data indicated that the hydride···σ-hole short contacts observed in the crystal structures of each compound have a purely noncovalent nature. The telluronium and iodonium cyanoborohydrides provide a significantly higher rate of the model reaction of imine hydrogenation compared with sodium and tetrabutylammonium cyanoborohydrides. Based on the NMR and high-resolution electrospray ionization mass spectrometry data indicating that the reaction progress is accompanied by the cation reduction, a mechanism involving intermediate formation of elusive onium hydrides has been proposed as an alternative to conventional electrophilic activation of the imine moiety by its ligation to the cation's σ-hole.
RESUMO
Kinetic data based on 1 H 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.