Solvated copper(I) hexafluorosilicate π-complexes based on [Cu2(amtd)2]2+ (amtd = 2-allylamino-5-methyl-1,3,4-thiadiazole) dimer

摘要

[Cu2(amdt)2]SiF6·C6H6 and [Cu2(amdt)2(H2O)2]SiF6·CH3CN·2H2O (amdt = 2-allylamino-5-methyl-1,3,4-thiadiazole) were obtained by alternating-current electrochemical synthesis,starting from water–acetonitrile–benzene mixtures containing 2-allylamino-5-methyl-1,3,4-thiadiazole and CuSiF6·4H2O. The electrochemical reduction of the saturated copperhexafluorosilicate water solution beneath the neatly poured layer of acetonitrile-benzeneamdt solution resulted in the formation of crystalline [Cu2(amdt)2]SiF6·C6H6. The initialstirring of the same mixture before subjecting it to the electrochemical reduction resulted inthe formation of [Cu2(amdt)2(H2O)2]SiF6·CH3CN·2H2O. A sluggish hydrolysis of theacetonitrile over 2 years in a closed test tube with [Cu2(amdt)2]SiF6·C6H6 crystals in amother liquor resulted in the formation of [Cu2L2(H2O)2]SiF6·CH3CONH2·2H2O. All thecompounds were studied using X-ray single-crystal diffraction and Raman spectroscopy.The molecular structures and the Raman spectra of the compounds were discussed on thebasis of computational modeling with the DFT/B3LYP/cc-pVDZ method.