Structures of Gd3N@C80 Prato Bis-Adducts: Crystal Structure, Thermal Isomerization, and Computational Studyстатья
Статья опубликована в высокорейтинговом журнале
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Дата последнего поиска статьи во внешних источниках: 4 сентября 2019 г.
Аннотация:The 1,3-dipolar cycloaddition of an azomethine ylide (Prato reaction) with M3N@Ih-C80 (denoted as M3N@C80; M = Sc, Lu, Y, Gd) was carried out to obtain fulleropyrrolidinebis(carboxylic acid) derivatives as scaffolds for the preparation of various functionalized M3N@C80 materials. The formation of two monoadduct isomers (the [6,6]- and [5,6]-adducts) were detected by HPLC
and identified by NMR and vis/NIR spectroscopies. In each Prato reaction with M3N@C80, the initial addition gave a [6,6]-adduct of the Ih-C80 cage, and subsequently, a [5,6]-adduct was obtained by complete or partial thermal isomerization via a rearrangement reaction. The reaction
rate of the latter thermal conversion of the adducts was dependent on the size of the metal cluster inside C80, and interestingly, in the reactions of Y3N@C80 and Gd3N@ C80, this conversion was found to be reversible for the first time. Detailed kinetic studies provided the enthalpy and
entropy barriers for the reactions of the adducts of Lu3N@C80, Y3N@C80, and Gd3N@C80. The utility of the obtained Prato adducts was confirmed by preparation of a highly water-soluble Gd3N@C80 derivative.