STUDIES ON THE INTERACTION OF SELENITE AND SELENIUM WITH SULFUR DONORS .5. THIOCYANATE

The oxidation of thiocyanic acid by selenous acid has been shown to ta ke place in an analogous way to that found for selenous acid oxidation of most thiols and thiolates to give the corresponding selenotrisulfi de and disulfide products. H2SeO3 + 4 HSCN = Se(SCN)(2) + NCSSCN + 2 H 2O The products of this reaction have been studied by IR, Raman, and S e-77, C-13, and N-15 NMR spectroscopy. The vibrational spectra of the solid Se(SCN)(2) have been assigned based on S-bonded thiocyanate liga nds and, through NMR and vibrational spectroscopy, both this linkage i somer and the isomer with N- and S-bonded thiocyanate have been identi fied and characterized in solutions of Se(SCN)(2). A complex combinati on of scalar relaxation processes, involving chemical exchange and qua drupolar effects, accounts for the line broadening observed in the car bon-13 NMR spectra.