Isolation of C1 through C4 derivatives from CO using heteroleptic uranium( iii ) metallocene aryloxide complexes - Archive ouverte HAL
Article Dans Une Revue Chemical Science Année : 2023

Isolation of C1 through C4 derivatives from CO using heteroleptic uranium( iii ) metallocene aryloxide complexes

Résumé

The conversion of C1 feedstock molecules such as CO into commodity chemicals is a desirable, but challenging, endeavour. When the U(iii) complex, [(C5Me5)(2)U(O-2,6-Bu-t(2)-4-MeC6H2)], is exposed to 1 atm of CO, only coordination is observed by IR spectroscopy as well as X-ray crystallography, unveiling a rare structurally characterized f element carbonyl. However, using [(C5Me5)(2)(MesO)U (THF)], Mes = 2,4,6-Me3C6H2, reaction with CO forms the bridging ethynediolate species, [{(C5Me5)(2)(MesO)U}(2)(mu(2)-OCCO)]. While ethynediolate complexes are known, their reactivity has not been reported in much detail to afford further functionalization. For example, addition of more CO to the ethynediolate complex with heating forms a ketene carboxylate, [{(C5Me5)(2)(MesO)U}(2)(mu(2):kappa(2):eta(1)-C3O3)], which can be further reacted with CO2 to yield a ketene dicarboxylate complex, [{(C5Me5)(2)(MesO)U}(2)(mu(2):kappa(2):kappa(2)-C4O5)]. Since the ethynediolate showed reactivity with more CO, we explored its reactivity further. A [2 + 2] cycloaddition is observed with diphenylketene to yield [{(C5Me5)(2)U}(2)(OC(CPh2)C(= O)CO)] with concomitant formation of [(C5Me5)(2)U(OMes)(2)]. Surprisingly, reaction with SO2 shows rare S-O bond cleavage to yield the unusual [(O2CC(O)(SO)](2-) bridging ligand between two U(iv) centres. All complexes have been characterized using spectroscopic and structural methods, and the reaction of the ethynediolate with CO to form the ketene carboxylate has been investigated computationally as well as the reaction with SO2.
Fichier principal
Vignette du fichier
ward_2023.pdf (930.69 Ko) Télécharger le fichier
Origine Fichiers éditeurs autorisés sur une archive ouverte

Dates et versions

hal-04218352 , version 1 (24-09-2024)

Identifiants

Citer

Robert Ward, Iker Del Rosal, Steven Kelley, Laurent Maron, Justin Walensky. Isolation of C1 through C4 derivatives from CO using heteroleptic uranium( iii ) metallocene aryloxide complexes. Chemical Science, 2023, 14 (8), pp.2024-2032. ⟨10.1039/d2sc06375a⟩. ⟨hal-04218352⟩
25 Consultations
2 Téléchargements

Altmetric

Partager

More