Intra- and intermolecular interception of a photochemically generated terminal uranium nitride

Abstract

Photolysis of the U(iv) azide LArU(NImDipp) generates a reactive uranium nitride intermediate that can be intercepted by nucleophilic substrates – the first example of intermolecular chemistry of a rare photochemically generated uranium nitride.

Actinide arene-metalates: ion pairing effects on the electronic structure of unsupported uranium–arenide sandwich complexes

“…, to stabilize a rare U-Fe bond and separately generate a highly reactive uranium-nitride species. 57,58 Regardless, the ancillary ligand coordination in these systems provides additional bonding contributions and potential ligand strain effects that can compete with or affect the actinide-arene bonding.…”

“…49 On this note, the use of tethered ligand manifolds to encourage supported actinide-arene interactions has become a popular approach within recent years. 47,48,[50][51][52][53][54][55][56][57][58][59] Bart, Meyer, and coworkers rst demonstrated that uranium-arene d-bonding was a key feature of their U(III) complex [( t Bu, t BuArO) 3 Mes]U, 50 while Arnold and coworkers showed that redox isomerization of the trans-calix [2]benzene [2]pyrollide (bz 2 pyr 2…”

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][17][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 21 and CO. 22 Among these complexes, the terminal U(V) nitride, [U(Tren TIPS )(N)]  (Tren TIPS = N(CH 2 CH 2 NSi i Pr 3 ) 3 ), is especially notable.…”

“…[23][24][25] However, widespread access to terminal actinide nitrides has proven elusive. 18,26 The majority of reported U(V) nitrides feature bridging nitride ligands that are capped by U(IV) ions, [27][28][29][30] which complicates the subsequent electronic structure analysis. 31 These observations point to the need for new synthetic routes to these materials, which would enable synthetic control over oxidation state, symmetry, and capping group identity.…”

“…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.…”