Reactions of Uranium Atoms with Ammonia: Infrared Spectra and Quasi-Relativistic Calculations of the U:NH3, H2N-UH, and HN=UH2 Complexes

Xuefeng Wang , Lester Andrews , Colin J. Marsden (1)

1 Chimie des éléments d & f (LCPQ)

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

Xuefeng Wang, Lester Andrews, Colin J. Marsden. Reactions of Uranium Atoms with Ammonia: Infrared Spectra and Quasi-Relativistic Calculations of the U:NH3, H2N-UH, and HN=UH2 Complexes. Chemistry - A European Journal, 2008, 14 (30), pp.9192-9201. ⟨10.1002/chem.200800875⟩. ⟨hal-00951059⟩