Uranium(III) redox chemistry assisted by a hemilabile bis(phenolate) cyclam ligand: uranium-nitrogen multiple bond formation comprising a trans-{RN═U(VI)═NR}(2+) complex.

A new monoiodide U(III) complex anchored on a hexadentate dianionic 1,4,8,11-tetraazacyclotetradecane-based bis(phenolate) ligand, [U(κ(6)-{((tBu2)ArO)2Me2-cyclam})I] (1), was synthesized from the reaction of [UI3(THF)4] (THF = tetrahydrofuran) and the respective potassium salt K2((tBu2)ArO)2Me2-cyclam and structurally characterized. Reactivity of 1 toward one-, two-, and four-electron oxidants was studied to explore the reductive chemistry of this new U(III) complex. Complex 1 reacts with one-electron oxidizers, such as iodine and TlBPh4, to form the seven-coordinate cationic uranium(IV) complexes [U(κ(6)-{((tBu2)ArO)2Me2-cyclam})I][X] (X = I (2-I), BPh4 (2-BPh4)). The new uranium(III) complex reacts with inorganic azides to yield the pseudohalide uranium(IV) complex [U(κ(6)-{((tBu2)ArO)2Me2-cyclam})(N3)2] (4) and the nitride-bridged diuranium(IV/IV) complex [(κ(4)-{((tBu2)ArO)2Me2-cyclam})(N3)U(μ-N)U(κ(5)-{((tBu2)ArO)2Me2-cyclam})] (5). Two equivalents of [U(κ(6)-{((tBu2)ArO)2Me2-cyclam})I] (1) effect the four-electron reduction of 1 equiv of PhN═NPh to form the bis(imido) complex [U(κ(4)-{((tBu2)ArO)2Me2-cyclam})(NPh)2] (6) and the U(IV) species 2-I. Moreover, the hemilability of the hexadentate ancillary ligand ((tBu2)ArO)2Me2-cyclam(2-) allows to perform the reductive cleavage of azobenzene with an unprecedented formation of a trans-bis(imido) complex. The complexes were characterized by NMR spectroscopy, and all the new uranium complexes were structurally authenticated by single-crystal X-ray diffraction.