INOR 323 |
| Interactions of the uranyl dication with anions constitute an important category of reactions in aqueous solutions at mid-to-high pH. The exact nature of the coordination and bonding is difficult to elucidate because of solvent effects and varying participation of uranium f-orbitals, and can be particularly intriguing for anions capable of multiple bonding modes. We have investigated intrinsic uranyl-anion interactions within discrete complex ions using Fourier transform mass spectrometry, wavelength-selective infrared multiple photon dissociation and density functional theory calculations to deduce structure. The bisulfate anion was studied because it possesses multiple strong IR-active absorptions that can provide insight into the nature of uranyl-anion bonding. IR spectra of three uranyl-bisulfate-acetone complex ions showed strong uranyl stretches that were red-shifted as the number of acetone ligands increased and surfuryl and carbonyl stretches that shifted to the blue. Experimentally measured IR spectra for the three complexes were in good general agreement with those predicted by density functional theory calculations. |
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Spectroscopy of Inorganic Systems
7:00 PM-10:00 PM, Sunday, August 19, 2007 BCEC -- Exhibit Hall - B2, Poster
Sci-Mix
Division of Inorganic Chemistry |