Infrared spectroscopy of extreme coordination: the carbonyls of U(+) and UO(2)(+) |
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Authors: | Ricks Allen M Gagliardi Laura Duncan Michael A |
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Institution: | Department of Chemistry, University of Georgia, Athens, Georgia 30602, United States. |
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Abstract: | Uranium and uranium dioxide carbonyl cations produced by laser vaporization are studied with mass-selected ion infrared spectroscopy in the C-O stretching region. Dissociation patterns, spectra, and quantum chemical calculations establish that the fully coordinated ions are U(CO)(8)(+) and UO(2)(CO)(5)(+), with D(4d) square antiprism and D(5h) pentagonal bipyramid structures. Back-bonding in U(CO)(8)(+) causes a red-shifted CO stretch, but back-donation is inefficient for UO(2)(CO)(5)(+), producing a blue-shifted CO stretch characteristic of nonclassical carbonyls. |
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