Dinitrogen Cleavage and Hydrogenation to Ammonia with a Uranium Complex

The Haber–Bosch process produces ammonia (NH3) from dinitrogen (N2) and dihydrogen (H2), but requires high temperature and pressure. Before iron-based catalysts were exploited in the current industrial Haber–Bosch process, uranium-based materials were used as effective catalysts for production of NH3 from N2. Although some molecular uranium complexes are capable of combining and even reducing N2, however, further hydrogenation with H2 to NH3 has not yet been reported. Here, we report the first example of N2 cleavage and hydrogenation with H2 to NH3 with a molecular uranium complex. The N2 cleavage product contains three uranium centers that are bridged by three imido μ2-NH ligands and one nitrido μ3-N ligand. Labeling experiments with 15N demonstrate that the nitrido ligand in the product originates from N2. Reaction of the N2-cleaved complex with H2 or H+ forms NH3 under mild conditions. A synthetic cycle has been established by the reaction of the N2-cleaved complex with TMSCl. The isolation of this trinuclear imido-nitrido product implies that a multimetallic uranium assembly plays an important role in the activation of N2.

Electrochemical Studies of Tris(cyclopentadienyl) Thorium and Uranium Complexes in the +2, +3, and +4 Oxidation States

Electrochemical measurements on tris(cyclopentadienyl) thorium and uranium compounds in the +2, +3, and +4 oxidation states are reported with C5H3(SiMe3)2, C5H4SiMe3, and C5Me4H ligands. The reduction potentials for both U and...

The synthesis and versatile reducing power of low-valent uranium complexes

This synthesis and diverse reactivity of uranium(iii) and uranium(ii) complexes is discussed.

Thorium(IV) and Uranium(IV) Phosphaazaallenes

The synthesis of tetravalent thorium and uranium complexes with the phosphaazaallene moiety, [N(tBu)C=P(C6H5)]2−, is described. The reaction of the bis(phosphido) complexes, (C5Me5)2An[P(C6H5)(SiMe3)]2, An = Th, U, with two equivalents of tBuNC produces (C5Me5)2An(CNtBu)[η2-(N,C)-N(tBu)C=P(C6H5)] with concomitant formation of P(SiMe3)2(C6H5) via silyl migration. These complexes are characterized by NMR and IR spectroscopy, as well as structurally determined using X-ray crystallography.

Density functional theory (DFT) calculations of VI/V reduction potentials of uranyl coordination complexes in non-aqueous solutions

Of particular interest within the +6 uranium complexes is the linear uranyl(vi) cation and it forms numerous coordination complexes in solution and exhibits incongruent redox behavior depending on coordinating ligands. This DFT study predicts VI/V reduction potentials of a range of uranyl(vi) complexes in non-aqueous solutions within ∼0.10−0.20 eV of experiment.

Tuning the structure, reactivity and magnetic communication of nitride-bridged uranium complexes with the ancillary ligands

The reactivity of the nitride ligand is increased in complexes of uranium(iv) when bound by the OSi(OtBu)3 ligand as opposed to N(SiMe3)2, but magnetic exchange coupling is decreased.