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Article Dans Une Revue Angewandte Chemie International Edition Année : 2016

Nucleophilic Reactivity of a Nitride‐Bridged Diuranium(IV) Complex: CO 2 and CS 2 Functionalization

Marta Falcone
  • Fonction : Auteur
Marinella Mazzanti
  • Fonction : Auteur

Résumé

Abstract Thermolysis of the nitride‐bridged diuranium(IV) complex Cs{(μ‐N)[U(OSi(O t Bu) 3 ) 3 ] 2 } ( 1 ) showed that the bridging nitride behaves as a strong nucleophile, promoting N−C bond formation by siloxide ligand fragmentation to yield an imido‐bridged siloxide/silanediolate diuranium(IV) complex, Cs{(μ‐N t Bu)(μ‐O 2 Si(O t Bu) 2 )U 2 (OSi(O t Bu) 3 ) 5 }. Complex 1 displayed reactivity towards CS 2 and CO 2 at room temperature that is unprecedented in f‐element chemistry, affording diverse N‐functionalized products depending on the reaction stoichiometry. The reaction of 1 with two equivalents of CS 2 yielded the thiocyanate/thiocarbonate complex Cs{(μ‐NCS)(μ‐CS 3 )[U(OSi(O t Bu) 3 ) 3 ] 2 } via a putative NCS − /S 2− intermediate. The reaction of 1 with one equivalent of CO 2 resulted in deoxygenation and N−C bond formation, yielding the cyanate/oxo complex Cs{(μ‐NCO)(μ‐O)[U(OSi(O t Bu) 3 ) 3 ] 2 }. Addition of excess CO 2 to 1 led to the unprecedented dicarbamate product Cs{(μ‐NC 2 O 4 )[U(OSi(O t Bu) 3 ) 3 ] 2 }.

Domaines

Chimie

Dates et versions

hal-04568623 , version 1 (05-05-2024)

Identifiants

Citer

Marta Falcone, Lucile Chatelain, Marinella Mazzanti. Nucleophilic Reactivity of a Nitride‐Bridged Diuranium(IV) Complex: CO 2 and CS 2 Functionalization. Angewandte Chemie International Edition, 2016, 55 (12), pp.4074-4078. ⟨10.1002/anie.201600158⟩. ⟨hal-04568623⟩
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