Reactivity of Open-Shell Metallofullerene Anions: Synthesis, Crystal Structures, and Electrochemical Properties of Benzylated Gd@C2v-C82

Zhou, Xinyi; Yao, Yang-Rong; Hu, Yajing; Yang, Le; Yang, Shaoting; Zhang, Yilu; Zhang, Qianyan; Peng, Ping; Jin, Peng; Li, Fang-Fang

doi:10.3390/inorganics11090349

Cited by 3 publications

(2 citation statements)

References 61 publications

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“…However, the one-electron reduction of La@ C 2 v -C 82 is effective for the activating its reactivity toward alkyl halides in the thermal reaction. Recently, Zhou et al reported that the reaction of Gd@ C 2 v -C 82 with benzyl bromide requires a three-electron reduction of Gd@ C 2 v -C 82 for the addition reaction to occur at room temperature [ 22 ].…”

Section: Resultsmentioning

confidence: 99%

Controlling the reactivity of La@C₈₂ by reduction: reaction of the La@C₈₂ anion with alkyl halide with high regioselectivity

Maeda,

Akita,

Suzuki

et al. 2023

Beilstein J. Org. Chem.

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Endohedral metallofullerenes have excellent redox properties, which can be used to vary their reactivity to certain classes of molecules, such as alkyl halides. In this study, the thermal reaction of the La@C2v-C82 anion with benzyl bromide derivatives 1 at 110 °C afforded single-bonded adducts 2–5 with high regioselectivity. The products were characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and visible–near infrared spectroscopy. The reaction of La@C2v-C82 with alkyl halides using the same conditions showed no consumption of La@C2v-C82, indicating that the reactivity of La@C2v-C82 toward alkyl halides was effectively increased by one-electron reduction. Single-crystal X-ray diffraction analysis of the single-bonded adduct 3a revealed the addition site of the p-methoxybenzyl group on La@C2v-C82. Theoretical calculations indicated that the addition site carbons in neutral La@C2v-C82 have high spin density, whereas those in the La@C2v-C82 anion do not have high charge densities. Thus, the reaction is believed to occur via electron transfer, followed by the radical coupling of La@C2v-C82 and benzyl radicals, rather than by bimolecular nucleophilic substitution reaction of La@C2v-C82 anion with 1.

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Section: Resultsmentioning

confidence: 99%

Controlling the reactivity of La@C₈₂ by reduction: reaction of the La@C₈₂ anion with alkyl halide with high regioselectivity

Maeda,

Akita,

Suzuki

et al. 2023

Beilstein J. Org. Chem.

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“…Lowering the reaction temperature requires an increase in the reactivity of EMF anions, which can be achieved by the reduction beyond the monoanionic state. Li et al showed that benzyl bromide reacts with the Gd@C 2v (9)-C 82 3trianion already at room temperature to give several isomers of Gd@C 82 (CH 2 Ph) [117].…”

Section: Redox-extraction and Derivatization Of Anionsmentioning

confidence: 99%

Capturing Unstable Metallofullerenes

Liu,

Popov

2024

Inorganics

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Metallofullerenes are interesting molecules with unique structures and physicochemical properties. After they are formed in the arc-discharge process, they are first buried in the carbon soot, which requires solvent extraction to fish them out, normally followed by HPLC separation. In this minireview, we summarize the main procedures developed to obtain pure metallofullerenes, including well-established extraction with conventional fullerene solvents followed by HPLC (procedure (I) as well as several methods developed for isolation and purification of unstable fullerenes insoluble in conventional fullerene solvents, including chemical modification followed by dissolution (II.1), chemical functionalization during extraction followed by HPLC (II.2), and chemical functionalization of ionic EMFs after redox-extraction followed by HPLC (procedure II.3). The main focus here is on procedure II.3, for which the current status and future perspective are discussed.

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Precision Chemistry of Metallofullerenes and Graphene: Recent Advances

Chang,

Chen,

Wei

2024

ChemPlusChem

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Precision chemistry of synthetic carbon allotropes including fullerene and graphene, characterized by a well‐controlled and spatially resolved addends bonding, has received widespread attention owing to its capability to tailor their physicochemical properties for high‐end applications. In the context of fullerene, particularly endohedral metallofullerenes (EMFs), precision chemistry emphasizes the regioselective binding of a specific number of moieties to the fullerene cage. In the case of graphene, precision chemistry focuses on achieving precise patterning and tailored modifications. Inspired by their intriguing advantages, the precision chemistry of these two members has witnessed rapid advancements. While existing reviews have outlined advancements in the precision chemistry of EMFs and graphene, this review uniquely concentrates on the most recent progress. Finally, the prospects in this field, with a special focus on the potential for creating functional materials through strategically patterned binding of fullerene and graphene networks are envisioned.

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Reactivity of Open-Shell Metallofullerene Anions: Synthesis, Crystal Structures, and Electrochemical Properties of Benzylated Gd@C2v-C82

Cited by 3 publications

References 61 publications

Controlling the reactivity of La@C₈₂ by reduction: reaction of the La@C₈₂ anion with alkyl halide with high regioselectivity

Controlling the reactivity of La@C₈₂ by reduction: reaction of the La@C₈₂ anion with alkyl halide with high regioselectivity

Capturing Unstable Metallofullerenes

Precision Chemistry of Metallofullerenes and Graphene: Recent Advances

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Reactivity of Open-Shell Metallofullerene Anions: Synthesis, Crystal Structures, and Electrochemical Properties of Benzylated Gd@C2v-C82

Cited by 3 publications

References 61 publications

Controlling the reactivity of La@C82 by reduction: reaction of the La@C82 anion with alkyl halide with high regioselectivity

Controlling the reactivity of La@C82 by reduction: reaction of the La@C82 anion with alkyl halide with high regioselectivity

Capturing Unstable Metallofullerenes

Precision Chemistry of Metallofullerenes and Graphene: Recent Advances

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Product

Resources

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Controlling the reactivity of La@C₈₂ by reduction: reaction of the La@C₈₂ anion with alkyl halide with high regioselectivity

Controlling the reactivity of La@C₈₂ by reduction: reaction of the La@C₈₂ anion with alkyl halide with high regioselectivity