Abstract
Cation-π complexes of the form UO(x)(+)(benzene) (x = 0, 1, 2) are produced by laser vaporization and cooled in a supersonic molecular beam. These ions are mass selected and studied with UV-visible laser photodissociation spectroscopy. Each of these complexes photodissociates by elimination of the benzene ligand. Above an energetic threshold, the absorption and photodissociation are continuous, indicating a high density of strongly coupled electronic states. The thresholds for the dissociation of each of these three complexes are measured and assigned as their respective bond dissociation energies. The bond energies determined [U(+)-(benzene): 42.5 ± 0.3 kcal/mol; UO(+)-(benzene): 41.0 ± 0.3 kcal/mol; UO(2)(+)-(benzene): 39.7 ± 0.3 kcal/mol] are comparable to those of transition metal ion-benzene complexes. Computational studies at the DFT/B3LYP level complement the experiments, predicting dissociation energies in reasonably good agreement with the experiments. Experiments and theory agree that the U(+)(benzene) complex is more strongly bound than its corresponding oxide ions. This new thermochemistry on actinide cation-π bonding should stimulate higher-level computational studies on these systems.