ИСТИНА

Combination of EPR and UV-Vis studies coupled with DFT calculations reveal that there are two chloroorganocuprates forming as a result of photolysis of quaternary ammonium tetrachlorocuprates in chloroorganic solvents (chlorobenzene, chloroform, and 2 chlorobutane) at 77 K. Calculated UV-Vis spectrum (TD-DFT/B(38HF)P86/aug-def2-TZVPP/COSMO) of [NR4+](R`)[CuCl2-] being scaled by 0.91 factor matches the experimental spectrum of the first complex, as well as calculated spectrum of [NR4+](R`)[CuCl32-] is similar to experimental spectrum of the second one. The same results were obtained for EPR spectra, in this case calculations were performed at B(38HF)P86/CP(PPP)/IGLO III/IGLO II level. Consequently, DFT calculations of spectral parameters of possible intermediates of photochemical reduction of chlorocuprates in organic solutions allow to establish the intermediates structures and to confirm the reaction mechanism.