Bingel-Hirsch reaction on actinidofullerene U@C2v(9)-C82: Improved regioselectivity compared to lanthanide
Daniel Torrens1, Bei Li2, Qin Wang2
1Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel lí Domingo 1, 43007 Tarragona, Spain.
Abstract:
Actinidofullerenes constitute a family of fullerenes that exhibit different metal-cage interactions, electronic structures, and properties compared to lanthanidofullerenes. In this study, we investigate the reactivity of mono-uranofullerene U@C2v(9)-C82 under the Bingel-Hirsch reaction and observe significantly higher regioselectivity, along with other differences in the reaction products, compared to La@C2v(9)-C82. Two products are obtained: a cycloadduct, which is the most abundant and has been characterized by x-ray crystallography, and a minor regioisomer that is most likely a single-bond product. Density functional theory calculations can explain the experimental structure and the formation of the two products and indicate that uranium is formally U(III) in both of them. The most abundant cycloadduct is formed under kinetic control, as found for other Bingel-Hirsch adducts, whereas the single-bond product is formed after oxidation of the anionic intermediate of the conventional Bingel-Hirsch reaction. This work is a new example of the unique reactivity and chemical properties of actinidofullerenes, which arise from their distinctive actinide-fullerene interactions.
More Related Videos
13:51Synthesis of Core-shell Lanthanide-doped Upconversion Nanocrystals for Cellular Applications
Published on: November 10, 2017
09:35Preparation of a Corannulene-functionalized Hexahelicene by CopperI-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units
Published on: September 18, 2016
Related Concept Videos
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
Photochemical Electrocyclic Reactions: Stereochemistry
Selection Rules: Photochemical Activation
Thermal Electrocyclic Reactions: Stereochemistry
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
