Uranium Nitrogen Multiple Bonding: Isostructural Anionic, Neutral, and Cationic Uranium Nitride Complexes Featuring a Linear U=N=U Core

Reaction of the uranium(III) tris(anilide) complex (THF)U(N[t-Bu]Ar)(3) (1, THF = tetrahydrofuran; Ar = 3,5-Me(2)C(6)H(3)) with MN(3) (M = Na, [N(n-Bu)(4)) results in the formation of the bimetallic diuranium(IV/IV) complexes M[(mu-N)(U(N[t-Bu]Ar)(3))(2)] (M[3]), which feature a single nitride ligand engaged as a linear, symmetric bridge between two uranium centers. The stability of the U=N=U core across multiple charge states is illustrated by stepwise chemical oxidation of Na[3] to the diuranium(IV/V) complex (mu-N)(U(N[t-Bu]Ar)(3))(2) (3) and the diuranium(V/V) complex [(mu-N)(U(N[t-Bu]Ar)(3))(2)][B(Ar(F))(4)] {[3][B(Ar(F))(4)]; Ar(F)= 3,5-(CF(3))(2)C(6)H(3)}. M[3], 3, and [3]B(Ar(F))(4)] were characterized by NMR spectroscopy. single-crystal X-ray diffraction, and elemental analysis. The cyclic voltammogram of 3 reveals two clean, reversible one-electron electrochemical events at E(1/2) = 1.69 and -0.67 V, assigned to the [3](-)/3 and 3/[3](+) redox couples. respectively. The X-ray crystal structures of [N(n-Bu(4))][3], 3, and [3][B3(Ar(F))(4)] reveal a linear U=N=U core that contracts by only similar to 0.03 angstrom A across the [3](n) (nr = -1, 0, +1) series, an effect that is rationalized as being primarily electrostatic in origin. [3][B(Ar(F))(4)] reacts with NaCN, eliminating Na[B(Ar(F))4] and forming the known diuranium(IV/IV) cyanoimide complex ([mu-NCN)(U(N[t-Bu]Ar)(3))(2), suggesting that the U=N=U core has metallonitrene-like character.