Reactions of Uranium Atoms with Ammonia: Infrared Spectra and Quasi-Relativistic Calculations of the U:NH3, H2N-UH, and HN=UH2 Complexes
Résumé
Ammonia molecules interact with U atoms, and the resulting U:NH3 complex rearranges upon visible irradiation to form the H2N-UH and HN=UH2 molecules in excess argon. These products are identified by functional group frequencies, 15NH3 and ND3 isotopic shifts, and comparison to frequencies calculated by using density functional theory. The N[DOUBLE BOND]U π bond in HN[DOUBLE BOND]UH2 is enhanced by partial triple-bond character through N(2p) to U(5f) conjugation, which is comparable to that found in the analogous HN[DOUBLE BOND]ThH2 molecule. These products also form complexes with additional ammonia molecules in the matrix. The interesting higher-energy N[TRIPLE BOND]UH3 complex is not formed