Reactivity of uranium(iii) with HE (E = S, Se, Te): synthesis of a series of mononuclear and dinuclear uranium(iv) hydrochalcogenido complexes.

We report the syntheses, electronic properties, and molecular structures of a series of mono- and dinuclear uranium(iv) hydrochalcogenido complexes supported by the sterically demanding but very flexible, single N-anchored tris(aryloxide) ligand (ArO)N). The mononuclear complexes [((ArO)N)U(DME)(EH)] (E = S, Se, Te) can be obtained from the reaction of the uranium(iii) starting material [((ArO)N)U(DME)] in DME reduction of HE and the elimination of 0.5 equivalents of H.

Uranium(III) complexes with bulky aryloxide ligands featuring metal-arene interactions and their reactivity toward nitrous oxide.

We report the synthesis and use of an easy-to-prepare, bulky, and robust aryloxide ligand starting from inexpensive precursor materials. Based on this aryloxide ligand, two reactive, coordinatively unsaturated U(III) complexes were prepared that are masked by a metal-arene interaction via δ-backbonding. Depending on solvent and uranium starting material, both a tetrahydrofuran (THF)-bound and Lewis-base-free U(III) precursor can easily be prepared on the multigram scale.

Reactivity of U-E-U (E = S, Se) toward CO2, CS2, and COS: new mixed-carbonate complexes of the types U-CO2E-U (E = S, Se), U-CS2E-U (E = O, Se), and U-COSSe-U.

We recently reported the formation of a bridging carbonate complex [{(((Ad)ArO)(3)N)U}(2)(μ-η(1):κ(2)-CO(3))] via reductive cleavage of CO(2), yielding a μ-oxo bridged complex, followed by the insertion of another molecule of CO(2). In a similar strategy, we were able to isolate and characterize a series of mixed carbonate complexes U-CO(2)E-U, U-CS(2)E-U, and even U-OC(S)Se-U, by reacting bridged chalcogenide complexes [{(((Ad)ArO)(3)N)U}(2)(μ-E)] (E = S, Se) with CO(2), CS(2), and COS. These chalcogenido mixed-carbonate complexes represent the first of their kind.

Observation of the inverse trans influence (ITI) in a uranium(V) imide coordination complex: an experimental study and theoretical evaluation.

An inverse trans influence has been observed in a high-valent U(V) imide complex, [(((Ad)ArO)(3)N)U(NMes)]. A thorough theoretical evaluation has been employed in order to corroborate the ITI in this unusual complex. Computations on the target complex, [(((Ad)ArO)(3)N)U(NMes)], and the model complexes [(((Me)ArO)(3)N)U(NMes)] and [(NMe(3))(OMe(2))(OMe)(3)U(NPh)] are discussed along with synthetic details and supporting spectroscopic data.