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Regioselective Radical Reaction of Monometallofullerene Y@C2v(9)-C82 With N-arylbenzamidine Mediated by Silver Carbonate.

ABSTRACT: A novel radical reaction of monometallofullerene Y@C2v(9)-C82 with N-arylbezamidine (1) is successfully conducted through catalysis with silver carbonate. The high-performance liquid chromatographic and mass spectrum results demonstrate that the reaction is highly regioselective to afford only one monoadduct (2) with an imidazoline group added on C82 cage, and computations through density functional theory reveal the addition group is attached to a specific [5, 6]-bond (C20-C76) near the Y atom. Furthermore, the analysis of prymidalization angle of the carbon atoms demonstrates the geometry of carbon cage is in favor of the regioselective formation of isomer (20, 76).

SUBMITTER: Li J

PROVIDER: S-EPMC7606928 | biostudies-literature | 2020

REPOSITORIES: biostudies-literature

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Regioselective Radical Reaction of Monometallofullerene Y@C2v(9)-C82 With N-arylbenzamidine Mediated by Silver Carbonate.

Li Jia J Yu Pengyuan P Lai Peng P Zou Jiajun J Liu Zhe Z Yi Xiuguang X Wang Wei W Pan Changwang C

Frontiers in chemistry 20201020

A novel radical reaction of monometallofullerene Y@C2v(9)-C82 with N-arylbezamidine (1) is successfully conducted through catalysis with silver carbonate. The high-performance liquid chromatographic and mass spectrum results demonstrate that the reaction is highly regioselective to afford only one monoadduct (2) with an imidazoline group added on C82 cage, and computations through density functional theory reveal the addition group is attached to a ...[more]

PMID: 33195099

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Project description:Chemical functionalization of endohedral metallofullerenes (EMFs) is essential for the application of these novel carbon materials. Actinide EMFs, a new EMF family member, have presented unique molecular and electronic structures but their chemical properties remain unexplored. Here, for the first time, we report the chemical functionalization of actinide EMFs, in which the photochemical reaction of Th@C 3v(8)-C82 and U@C 2v(9)-C82 with 2-adamantane-2,3'-[3H]-diazirine (AdN2, 1) was systematically investigated. The combined HPLC and MALDI-TOF analyses show that carbene addition by photochemical reaction afforded three isomers of Th@C 3v(8)-C82Ad and four isomers of U@C 2v(9)-C82Ad (Ad = adamantylidene), presenting notably higher reactivity than their lanthanide analogs. Among these novel EMF derivatives, Th@C 3v(8)-C82Ad(I, II, III) and U@C 2v(9)-C82Ad(I, II, III) were successfully isolated and were characterized by UV-vis-NIR spectroscopy. In particular, the molecular structures of first actinide fullerene derivatives, Th@C 3v(8)-C82Ad(I) and U@C 2v(9)-C82Ad(I), were unambiguously determined by single crystal X-ray crystallography, both of which show a [6,6]-open cage structure. In addition, isomerization of Th@C 3v(8)-C82Ad(II), Th@C 3v(8)-C82Ad(III), U@C 2v(9)-C82Ad(II) and U@C 2v(9)-C82Ad(III) was observed at room temperature. Computational studies suggest that the attached carbon atoms on the cages of both Th@C 3v(8)-C82Ad(I) and U@C 2v(9)-C82Ad(I) have the largest negative charges, thus facilitating the electrophilic attack. Furthermore, it reveals that, compared to their lanthanide analogs, Th@C 3v(8)-C82 and U@C 2v(9)-C82 have much closer metal-cage distance, increased metal-to-cage charge transfer, and strong metal-cage interactions stemming from the significant contribution of extended Th-5f and U-5f orbitals to the occupied molecular orbitals, all of which give rise to their unusual high reactivity. This study provides first insights into the exceptional chemical properties of actinide endohedral fullerenes, which pave ways for the future functionalization and application of these novel EMF compounds.

Dataset Information

Regioselective Radical Reaction of Monometallofullerene Y@C2v(9)-C82 With N-arylbenzamidine Mediated by Silver Carbonate.

Publications

Regioselective Radical Reaction of Monometallofullerene Y@C<sub>2v</sub>(9)-C<sub>82</sub> With N-arylbenzamidine Mediated by Silver Carbonate.

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