Inverse Electron Demand Diels-Alder Reaction on M3N@C80 (M=Lu, Sc): Reactivity and Reversibility Enable Chemical Separation of Metallofullerenes

被引：0

作者：

Sun, Yue ^{[1
]}

Abella, Laura ^{[2
]}

Emge, Thomas J. ^{[1
]}

Zhu, Sheng ^{[1
]}

Li, Yanbang ^{[1
]}

Ferraro, Ian ^{[3
]}

Li, Anyin ^{[3
]}

Stevenson, Steven ^{[4
,5
]}

Poblet, Josep M. ^{[2
]}

Rodriguez-Fortea, Antonio ^{[2
]}

Zhang, Jianyuan ^{[1
]}

机构：

[1] Rutgers State Univ, Dept Chem & Chem Biol, 123 Bevier Rd, Piscataway, NJ 08854 USA

[2] Univ Rovira i Virgili, Dept Quim Fis & Inorgan, Marcel Li Domingo 1, Tarragona 43007, Spain

[3] Univ New Hampshire, Dept Chem, 23 Acad Way, Durham, NH 03824 USA

[4] Purdue Univ Ft Wayne, Dept Chem & Biochem, Ft Wayne, IN 46805 USA

[5] Purdue Univ Ft Wayne, Mol Ctr 1, Ft Wayne, IN 46805 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2025年

基金：

美国国家科学基金会;

关键词：

endohedral fullerenes; cycloaddition; density functional calculations; chemical separation; crystallography; ENDOHEDRAL METALLOFULLERENES; CRYSTALLOGRAPHIC CHARACTERIZATION; RETRO-CYCLOADDITION; ENHANCED REACTIVITY; SC3N-AT-C-80; PURIFICATION; METAL; LU; FULLERENES; ISOMERS;

D O I：

10.1002/anie.202424776

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Endohedral metallofullerenes are chemically more inert compared to empty fullerenes, primarily due to their intramolecular electron transfer. In this work, we report an inverse electron demand Diels-Alder (IEDDA) reaction on M3N@C80 (M=Lu, Sc), where they show significantly higher reactivity than empty fullerenes. The molecular structures of the [4+2] cycloadducts were unambiguously characterized. Moreover, the cycloadducts can fully revert to pristine M3N@C80 via retro-cycloaddition upon thermal treatment. With the unusual reactivity and reversibility, the IEDDA reaction enables an effective separation approach for metallofullerenes from their soot extracts, opening path to efficient and economical scale-up synthesis of metallofullerenes in laboratory and industrial settings.

引用

页数：9

共 22 条

[21] Metal ion size and the pyramidalization of trimetallic nitride units inside a fullerene cage: Comparisons of the crystal structures of M3N@Ih-C80 (M = Gd, Tb, Dy, Ho, Er, Tm, Lu, and Sc) and some mixed metal counterparts
Olmstead, Marilyn M.
Zuo, Tianming
Dorn, Harry C.
Li, Tinghui
Balch, Alan L.
INORGANICA CHIMICA ACTA, 2017, 468 : 321 - 326
[22] Single-Molecule Magnets DyM2N@C80 and Dy2MN@C80 (M=Sc, Lu): The Impact of Diamagnetic Metals on Dy3+ Magnetic Anisotropy, Dy••Dy Coupling, and Mixing of Molecular and Lattice Vibrations
Spree, Lukas
Schlesier, Christin
Kostanyan, Aram
Westerstroem, Rasmus
Greber, Thomas
Buechner, Bernd
Avdoshenko, Stanislav M.
Popov, Alexey A.
CHEMISTRY-A EUROPEAN JOURNAL, 2020, 26 (11) : 2436 - 2449

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