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Review
. 2020 Aug 10;25(16):3626.
doi: 10.3390/molecules25163626.

New Horizons in Chemical Functionalization of Endohedral Metallofullerenes

Michio Yamada  1 , Michael T H Liu  2 , Shigeru Nagase  3 , Takeshi Akasaka  1   4   5   6
Affiliations
Review

New Horizons in Chemical Functionalization of Endohedral Metallofullerenes

Michio Yamada et al. Molecules. .

Abstract

This overview explains some new aspects of chemical functionalization of endohedral metallofullerenes (EMFs) that have been unveiled in recent years. After differences in chemical reactivity between EMFs and the corresponding empty fullerenes are discussed, cage-opening reactions of EMFs are examined. Then, the selective bisfunctionalization of EMFs is explained. Finally, single-bonding derivatization of EMFs is addressed. The diversity and applicability of the chemical functionalization of endohedral metallofullerenes are presented to readers worldwide.

Keywords: addition reactions; carbenes; chemical functionalization; electrochemistry; endohedral metallofullerene; fullerene; lanthanide ions; nanocarbon; pericyclic reactions; radicals.

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Conflict of interest statement

The authors have no conflict of interest to declare.

Figures

Figure 1
Figure 1
(a) Photochemical reaction of C84 and 1. (b) Photochemical reaction of C84 and 3. (c) Photochemical reaction of Sc2C2@C84 and 1. (d) Photochemical reaction of Sc2C2@C84 and 3.
Figure 2
Figure 2
Cycloaddition reaction of Sc3N@C80 with 2-amino-4,5-diisopropoxybenzoic acid and isoamyl nitrite, to produce open-cage metallofullerene 7.
Figure 3
Figure 3
Cage-opening reaction of La2@C72 with 5,6-diphenyl-3-(2-pyridyl)-1,2,4-triazine.
Figure 4
Figure 4
Bisfunctionalization of EMFs. (a) Photochemical reaction of La2@C72 and 1. (b) Two-step bisfunctionalization of La2@C80. (c) Two-step bisfunctionalization of Lu3N@C80. (d) Prato reaction of Gd3N@C80 with N-ethylglycine and paraformaldehyde.
Figure 5
Figure 5
(a) Reaction of La2@C80 with 3-chloro-5,6-diphenyltriazine, and reaction of 15 with toluene. (b) Benzylation of M2@C80. (c) Schematic description of the single-electron reduction and oxidation of M2@C80(CH2Ph).
Figure 6
Figure 6
(a) Reactions of Sc3N@C80 with 1,3-bis(diisopropylphenyl)-imidazol-2-ylene in the absence or presence of oxygen. (b) Reactions of Sc3N@C80 with in situ generated SHCs.
See this image and copyright information in PMC

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