Abstract
Attenuated total reflectance infrared (ATR-IR) and Raman spectroscopies are used to identify the complexed species of mercury(II) with acetate and some aliphatic derivatives in aqueous solutions, as a function of pH and metal-to-acetate ratio. The spectra of the free carboxylate ions, in their sodium salt solutions, and of the protonated molecules are shown for comparison and assigned below 1800 cm-1. Whatever the stoichiometries assumed [HgCH<sub>3</sub>COO+ up to Hg(CH<sub>3</sub>COO)<sub>4</sub>2-], one structure is observed, principally via the stretching modes upsilon(CO<sub>2</sub>) and upsilon (CC), although two strong bands have a upsilon<sub>s</sub>(CO<sub>2</sub>) character owing to an accidental coupling of this mode with delta<sub>s</sub>(CH<sub>3</sub>) in all the acetate complexes. This coupling is demonstrated with the isotopic ligand CD<sub>3</sub>COO, which displays only one upsilon<sub>s</sub>(CO<sub>2</sub>) band on account of the separation of this mode from delta<sub>s</sub>(CD<sub>3</sub>). The splitting between upsilon<sub>a</sub>(CO<sub>2</sub>) and upsilon<sub>s</sub>(CO<sub>2</sub>) increases up to about 260 cm-1 for all the carboxylates under study, the value pointing to a hydrated monodentate form.
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