Intra- and intermolecular interception of a photochemically generated terminal uranium nitride

The photochemically generated synthesis of a terminal uranium nitride species is here reported and an examination of its intra- and intermolecular chemistry is presented. Treatment of the U(iii) complex L^ArUI(DME) ((L^Ar)^2- = 2,2''-bis(Dippanilide)-p-terphenyl; Dipp = 2,6-diisopropylphenyl) with LiNIm^Dipp ((NIm^Dipp)^- = 1,3-bis(Dipp)-imidazolin-2-iminato) generates the sterically congested 3N-coordinate compound L^ArU(NIm^Dipp) (1). Complex 1 reacts with 1 equiv. of Ph₃CN₃ to give the U(iv) azide L^ArU(N₃)(NIm^Dipp) (2). Structural analysis of 2 reveals inequivalent N_α-N_β > N_β-N_γ distances indicative of an activated azide moiety predisposed to N₂ loss. Room-temperature photolysis of benzene solutions of 2 affords the U(iv) amide (N-L^Ar)U(NIm^Dipp) (3) via intramolecular N-atom insertion into the benzylic C-H bond of a pendant isopropyl group of the (L^Ar)^2- ligand. The formation of 3 occurs as a result of the intramolecular interception of the intermediately generated, terminal uranium nitride (L^Ar)U(N)(NIm^Dipp) (3'). Evidence for the formation of 3' is further bolstered by its intermolecular capture, accomplished by photolyzing solutions of 2 in the presence of an isocyanide or PMe₃ to give (L^Ar)U[NCN(C₆H₃Me₂)](NIm^Dipp) (5) and (N,C-L^Ar*)U(N[double bond, length as m-dash]PMe₃)(NIm^Dipp) (6), respectively. These results expand upon the limited reactivity studies of terminal uranium-nitride moieties and provide new insights into their chemical properties.