Intra- and intermolecular interception of a photochemically generated terminal uranium nitride†
| العنوان: | Intra- and intermolecular interception of a photochemically generated terminal uranium nitride† |
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| المؤلفون: | Alejandro J. Metta-Magaña, Munendra Yadav, Skye Fortier |
| المصدر: | Chemical Science |
| بيانات النشر: | The Royal Society of Chemistry, 2020. |
| سنة النشر: | 2020 |
| مصطلحات موضوعية: | Steric effects, chemistry.chemical_compound, Chemistry, chemistry, Isocyanide, Amide, Intramolecular force, Moiety, Reactivity (chemistry), General Chemistry, Azide, Medicinal chemistry, Isopropyl |
| الوصف: | The photochemically generated synthesis of a terminal uranium nitride species is here reported and an examination of its intra- and intermolecular chemistry is presented. Treatment of the U(iii) complex LArUI(DME) ((LAr)2− = 2,2′′-bis(Dippanilide)-p-terphenyl; Dipp = 2,6-diisopropylphenyl) with LiNImDipp ((NImDipp)− = 1,3-bis(Dipp)-imidazolin-2-iminato) generates the sterically congested 3N-coordinate compound LArU(NImDipp) (1). Complex 1 reacts with 1 equiv. of Ph3CN3 to give the U(iv) azide LArU(N3)(NImDipp) (2). Structural analysis of 2 reveals inequivalent Nα–Nβ > Nβ–Nγ distances indicative of an activated azide moiety predisposed to N2 loss. Room-temperature photolysis of benzene solutions of 2 affords the U(iv) amide (N-LAr)U(NImDipp) (3) via intramolecular N-atom insertion into the benzylic C–H bond of a pendant isopropyl group of the (LAr)2− ligand. The formation of 3 occurs as a result of the intramolecular interception of the intermediately generated, terminal uranium nitride (LAr)U(N)(NImDipp) (3′). Evidence for the formation of 3′ is further bolstered by its intermolecular capture, accomplished by photolyzing solutions of 2 in the presence of an isocyanide or PMe3 to give (LAr)U[NCN(C6H3Me2)](NImDipp) (5) and (N,C-LAr*)U(N Created by potrace 1.16, written by Peter Selinger 2001-2019 PMe3)(NImDipp) (6), respectively. These results expand upon the limited reactivity studies of terminal uranium–nitride moieties and provide new insights into their chemical properties. 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. |
| اللغة: | English |
| تدمد: | 2041-6539 2041-6520 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::032dff6ab103fd5f7d0a3eab171a3a39 http://europepmc.org/articles/PMC8157337 |
| Rights: | OPEN |
| رقم الانضمام: | edsair.doi.dedup.....032dff6ab103fd5f7d0a3eab171a3a39 |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 20416539 20416520 |
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