Synthesis, structure, and reactivity of uranium(vi) nitrides

Abstract

Uranium nitride compounds are important molecular analogues of uranium nitrides materials such as UN and UN2 which are effective catalysts in the Haber-Bosch synthesis of ammonia, but the synthesis of...

Uranium–nitride chemistry: uranium–uranium electronic communication mediated by nitride bridges

“…{X n UNUX n } or {X n UNA} (X = monoanionic donor centre, mono- or polydentate ligands; A = Lewis acid acceptor group), 7 whereas for high (+5, +6) oxidation states of uranium the bridging ‘diamond-core’ dinitride motif {X n U(μ-N) 2 UX n } is usually found. 8 To date, however, mid- or low-oxidation state ‘diamond-core’ dinitrides are rare, being restricted to trivalent binary U III 2 N 2 studied in cryogenic matrix isolation experiments, 9 a molecular tetrauranium( iv )–dirhodium cluster, 10 a mixed-valent diuranium( IV/V )–calix[4]tetrapyrrole complex, 11 and a tetrauranium( iv ) cluster. 12 There are, however, no examples of diuranium( iv ) complexes exhibiting the ‘diamond-core’ dinitride motif.…”

Synthesis of a heterobimetallic actinide nitride and an analysis of its bonding

“…Moreover, complexes containing An N bonds are known to mediate a variety of important and challenging small molecule transformations. 16–18 For example, Mazzanti's U( iii ) nitride [K 3 {U(OSi(O t Bu) 3 ) 3 } 2 (μ-N)] is able to mediate the capture and functionalization of N 2 . 19,20 Likewise, the U( iv ) nitride, [Cs{U(OSi(O t Bu) 3 ) 3 } 2 (μ-N)], can activate both H 2 (ref.…”

“…These reactions are unique because they use NH 3 as the nitride source, instead of [N 3 ] − , which is typically the nitrogen source used to form actinide nitrides. 16,18,26 Thus, we hypothesized that a similar synthetic approach could be used to generate a uranium nitride with the desired oxidation state and symmetry properties.…”

Photochemical Synthesis of Transition Metal-Stabilized Uranium(VI) Nitride Complexes

“…The combination of late transition metal (Rh and Ir) in U(V) nitrides 4 and U(VI) nitrides 5 are different from the main group borane-capped U(VI) nitride 47 or another uranium-stabilized U(VI) nitrides 48 , 49 . Consequently, the stabilities of the newly synthesized uranium nitrides 4 and 5 were investigated.…”

“…The introduction of the main group element or another uranium center is an effective method to stabilize the U(VI) nitrides 47 – 49 . For instance, the Cummins group reported a borane-capped U(VI) nitride complex by chemical oxidation of the U(V) nitridoborate complex 47 .…”