Infrared Spectroscopy of Extreme Coordination: The Carbonyls of U+ and UO2+

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 UO2(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 UO2(CO)(5)(+), producing a blue-shifted CO stretch characteristic of nonclassical carbonyls.