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

Article abstract of DOI:10.1016/j.jorganchem.2016.03.001

[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 copper hexafluorosilicate water solution beneath the neatly poured layer of acetonitrile-benzene amdt solution resulted in the formation of crystalline [Cu₂(amdt)₂]SiF₆·C₆H₆. The initial stirring of the same mixture before subjecting it to the electrochemical reduction resulted in the formation of [Cu₂(amdt)₂(H₂O)₂]SiF₆·CH₃CN·2H₂O. A sluggish hydrolysis of the acetonitrile over 2 years in a closed test tube with [Cu₂(amdt)₂]SiF₆·C₆H₆ crystals in a mother liquor resulted in the formation of [Cu₂L₂(H₂O)₂]SiF₆·CH₃CONH₂·2H₂O. All the compounds were studied using X-ray single-crystal diffraction and Raman spectroscopy. The molecular structures and the Raman spectra of the compounds were discussed on the basis of computational modeling with the DFT/B3LYP/cc-pVDZ method.