title: Uranium azide photolysis results in C-H bond activation and provides evidence for a terminal uranium nitride.
abstract: Uranium nitride [U[triple bond]N](x) is an alternative nuclear fuel that has great potential in the expanding future of nuclear power; however, very little is known about the U[triple bond]N functionality. We show, for the first time, that a terminal uranium nitride complex can be generated by photolysis of an azide (U-N=N=N) precursor. The transient U[triple bond]N fragment is reactive and undergoes insertion into a ligand C-H bond to generate new N-H and N-C bonds. The mechanism of this unprecedented reaction has been evaluated through computational and spectroscopic studies, which reveal that the photochemical azide activation pathway can be shut down through coordination of the terminal azide ligand to the Lewis acid B(C(6)F(5))(3). These studies demonstrate that photochemistry can be a powerful tool for inducing redox transformations for organometallic actinide complexes, and that the terminal uranium nitride fragment is reactive, cleaving strong C-H bonds.
authors: Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA.
authors: Robert K
authors: RK
authors: Thomson
authors: Thibault
authors: T
authors: Cantat
authors: Brian L
authors: BL
authors: Scott
authors: David E
authors: DE
authors: Morris
authors: Enrique R
authors: ER
authors: Batista
authors: Jaqueline L
authors: JL
authors: Kiplinger
mesh_terms: D001386:Azides / Q000138:chemical synthesis / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D017672:Nitrogen Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D009678:Nuclear Energy; D010084:Oxidation-Reduction; D010782:Photolysis; D013055:Spectrophotometry, Infrared; D017974:Uranium Compounds / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D001386:Azides; D017672:Nitrogen Compounds; D017974:Uranium Compounds