Spectrochemistry of solutions. Part 14. Raman and infrared spectra of thiocyanatosilver(I) complexes in some non-aqueous solutions

Abstract
Infrared and Raman spectra have shown that, when Ag+ is complexed by SCN, the species present and the equilibrium steps involved are solvent specific. In pyridine, complexation of Ag+ by SCN passes through [Ag2(SCN)]+ and AgSCN to [Ag(SCN)2]. Only AgSCN and [Ag(SCN)2] have been identified in tetrahydrofuran, dimethyl sulphoxide, and acetone, and only [Ag(SCN)2] was found in propylene carbonate. Solutions in dimethylformamide and dimethylacetamide at high [SCN]/[Ag+] ratios contain a small proportion of the SCN in the bridged complex [Ag2(SCN)3], but in trimethyl phosphate the SCN is approximately equally distributed between [Ag2(SCN)3] and [Ag(SCN)2]. The spectra of thiocyanatosilver(I) complexes in hexamethylphosphoramide differ from those of all the other solutions; no linear [Ag(SCN)2] complex is found and two feasible explanations of the spectra are offered. No complex higher than [Ag(SCN)2] occurs in any of these solutions.

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