Nitride protonation and NH3 binding versus N–H bond cleavage in uranium nitrides

Abstract

The conversion of metal nitrides to NH₃ is an essential step in dinitrogen fixation, but there is limited knowledge of the reactivity of nitrides with protons (H⁺). Herein, we report comparative studies for the reactions of H⁺ and NH₃ with uranium nitrides, containing different types of ancillary ligands. We show that the differences in ancillary ligands, leads to dramatically different reactivity. The nitride group, in nitride-bridged cationic and anionic diuranium(IV) complexes supported by –N(SiMe₃)₂ ligands, is resistant toward protonation by weak acids, while stronger acids result in ligand loss by protonolysis. Moreover, the basic –N(SiMe₃)₂ ligands promote the N–H heterolytic bond cleavage of NH₃, yielding a “naked” diuranium complex containing three bridging ligands, a nitride (N³⁻) and two NH₂ ligands. Conversely, in the nitride-bridged diuranium(IV) complex supported by –OSi(O^tBu)₃ ligands, the nitride group is easily protonated to afford NH₃, which binds the U(IV) ion strongly, resulting in a mononuclear U–NH₃ complex, where NH₃ can be displaced by addition of strong acids. Furthermore, the U–OSi(O^tBu)₃ bonds were found to be stable, even in the presence of stronger acids, such as NH₄BPh₄, therefore indicating that –OSi(O^tBu)₃ supporting ligands are well suited to be used when acidic conditions are required, such as in the H⁺/e⁻ mediated catalytic conversion of N₂ to NH₃.