Electrochemical reduction of some methanofullerenes. On the mechanism of the retro-Bingel reaction

Нуретдинов, И. А.; Yanilkin, V. V.; Gubskaya, V. P.; Mahsimyuk, N. I.; Berezhnaya, L. Sh.

doi:10.1007/bf02494770

Cited by 11 publications

(12 citation statements)

References 16 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, controlled-potential electrolysis of 42 (0.79 e/molecule) followed by quenching with an excess of CH 3 I yielded a clear m/z ϭ 2081 peak by MALDI mass spectrometry, consistent with dimer formation, with the additional incorporation of two methyl groups, molecular oxygen, and sodium. Multiple experiments provided similar results with mass spectral peaks with m/z ratios that evidenced the formation of dimeric [70]fullerene structures (m/z Ͼ 1700). [23] On the basis of the results summarized in this section, we proposed a mechanism for the retro-cyclopropanation reaction that involves the heterolytic opening of the cyclopropane ring leading to charge formation either in the fullerene core or in the addend, and that these interconvert at equilibrium.…”

supporting

confidence: 80%

“…Future applications in the preparation of unusual derivatives with controlled regiochemistry, particularly for C 70 and higher fullerenes derivatives, remain unexplored. …”

Section: Discussionmentioning

confidence: 99%

“…Upon re-oxidation and product analysis, an 82% yield of pure C 60 was obtained, and the new electrochemically induced reaction which efficiently removed the cyclopropane ring adduct was called the retro-Bingel reaction. [21,22] In order to test the generality of the new electrolytic reaction, in addition to the experiments mentioned with bisadducts 7Ϫ12, a mono bis(ethoxycarbonyl)methano-C 70 was also investigated following the same electrolysis protocol. Purification of the solution after coulometric reduction (which requires a net charge transfer of four electrons per molecule) followed by oxidation, resulted in a 70% yield of isolated C 70 .…”

Section: Removal Of the Methano-addends: The Retro-bingel Reactionmentioning

confidence: 99%

“…[21,22] In order to test the generality of the new electrolytic reaction, in addition to the experiments mentioned with bisadducts 7Ϫ12, a mono bis(ethoxycarbonyl)methano-C 70 was also investigated following the same electrolysis protocol. Purification of the solution after coulometric reduction (which requires a net charge transfer of four electrons per molecule) followed by oxidation, resulted in a 70% yield of isolated C 70 . This conversion occurred stepwise as new waves between 0 and Ϫ0.5 V vs. Ag started to appear during electrolysis, providing evidence for the formation of intermediates.…”

Section: Removal Of the Methano-addends: The Retro-bingel Reactionmentioning

confidence: 99%

See 3 more Smart Citations

Electrochemically Induced Retro‐Cyclopropanation Reactions

2004

View full text Add to dashboard Cite

The efficient removal of methano addends from fullerenes using reductive electrochemistry is a versatile and useful reaction, which was initially called the retro-Bingel reaction since it was observed for the first time on bis(alkoxycarbonyl)methano adducts, commonly known as Bingel adducts. Since its initial discovery, this reaction has been successfully employed in the separation of enantiomers and constitutional isomers of fullerenes, which in some cases were otherwise not accessible. Even more interesting than the retro-Bingel reaction was the electrochemically induced isomerization that bis-methano adducts of C 60 exhibit, and which was referred to as the ''shuffle''. The combination of both reactions gave interesting results during the electrolysis of tetrakis-, pentakis-, and hexakis-Bingel adducts of C 60 . The selective removal of Bingeltype addends, while leaving other addends undisturbed, was also investigated. More recently, it was observed that in addition to bis(alkoxycarbonyl)methano adducts, electrochemical Spain in 1972. She received her B.Sc., M.Sc., and PhD degrees in 1995 MICROREVIEWS: This feature introduces the readers to the authors' research through a concise overview of the selected topic. Reference to important work from others in the field is included. reduction of other methano adducts, such as spiromethanofullerenes, could also result in removal of the methano addends, thus the reaction was more generally denoted as retro-cyclopropanation. In some of the spiromethanofullerenes investigated, and depending on the solvent used, an electrochemically induced intermolecular addend transfer was observed, which provided a regioisomeric distribution that differed significantly from that obtained by a synthetic route. We have recently shown that singly bonded dimers are formed as intermediates during retro-cyclopropanation reactions. In this microreview, we describe the general observations that led to the initiation of these exciting electrochemical investigations, review the differences between the chemical and electrochemical methodologies in retro-cyclopropanation reactions and explore the mechanisms involved during addend removal.

show abstract

supporting

confidence: 80%

“…Future applications in the preparation of unusual derivatives with controlled regiochemistry, particularly for C 70 and higher fullerenes derivatives, remain unexplored. …”

Section: Discussionmentioning

confidence: 99%

Section: Removal Of the Methano-addends: The Retro-bingel Reactionmentioning

confidence: 99%

Section: Removal Of the Methano-addends: The Retro-bingel Reactionmentioning

confidence: 99%

See 2 more Smart Citations

Electrochemically Induced Retro‐Cyclopropanation Reactions

2004

View full text Add to dashboard Cite

show abstract

“…The structures of these compounds were completely confirmed by physicochemical methods (UV, IR, and 1 H, 13 C, and 31 P NMR spectroscopy).…”

Section: Resultsmentioning

confidence: 98%

Synthesis and structures of new C60 fullerene derivatives containing carbonyl groups

et al. 2005

Self Cite

View full text Add to dashboard Cite

The reactions of fullerene C 60 with substituted haloketones, including organophosphorus haloketones, in the presence of bases afforded new methanofullerenes containing carbonyl or carbonyl and acetal groups. The structures of the resulting compounds were established by spectroscopic methods. Their electrochemical reduction and oxidation were studied by cyclic voltammetry and ESR spectroscopy. The three dimensional structures were calculated by the PM3 and DFT/PBE/TZ2P methods.

show abstract

Mechanisms of Electrochemically‐Induced Retro‐Cyclopropanation Reactions of Fullerene Derivatives Using Digital Simulations

Carano

Echegoyen

2003

Chemistry A European J

View full text Add to dashboard Cite

Three C(60) derivatives, 1, 2 and 3, have been studied by cyclic voltammetry (CV) under high vacuum in anhydrous tetrahydrofuran (THF). The CV behavior was essentially similar to that already observed for other cyclopropanated fullerene derivatives. After the second reduction processes all compounds undergo a chemical reaction that generates another electroactive species. This "new" chemical species is likely to be the compound with the cyclopropane ring open. Differences in CV behavior were observed for the different addends. Electrochemical data obtained at different scan rates for a given potential window, were fit with the BAS digital simulation program, DigiSim. The purpose of this study was to probe the proposed mechanisms and to obtain reliable estimations of the kinetic constants for the homogeneous chemical reactions taking place during the CV experiments. Calculations at the PM3 level lend additional support to the conclusions derived from digital simulations. The proposed mechanism is similar for all the compounds and involves two main chemical reactions in a reversible square scheme.

show abstract

Electrochemical reduction of some methanofullerenes. On the mechanism of the retro-Bingel reaction

Cited by 11 publications

References 16 publications

Electrochemically Induced Retro‐Cyclopropanation Reactions

Electrochemically Induced Retro‐Cyclopropanation Reactions

Synthesis and structures of new C60 fullerene derivatives containing carbonyl groups

Mechanisms of Electrochemically‐Induced Retro‐Cyclopropanation Reactions of Fullerene Derivatives Using Digital Simulations

Contact Info

Product

Resources

About