Preferential Site of Attack on Fullerene Cations:  Frontier Orbitals and Rate Coefficients

Lee, Kee Hag; Lee, Chang‐Hoon; Kang, Jin Kyu; Lee, Won Jin; Lee, Sang Kuk; Böhme, Diethard K.

doi:10.1021/jp0652749

Cited by 15 publications

(8 citation statements)

References 18 publications

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“…Moreover, in contrast with corannulene, there is no well‐defined decrease of pyramidalization with reduction. On the other hand, the POAV1 angles found for altan-1 and its ions are comparable with those of C 80 6− and other stable fullerenes, and thus cannot be considered as a major problem for their synthesis.…”

Section: Resultsmentioning

confidence: 91%

Anionic derivatives of altan‐corannulene

Monaco

Zanasi

2013

J of Physical Organic Chem

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We report computations of excitation energies, magnetizabilities, and current strengths for the dianion, tetraanion, and hexaanion of the previously introduced altan-corannulene, a molecule designed to hold a strong paratropic current. None of these ions has a fully diatropic or paratropic pattern: dianion and tetraanion both have a paratropic/diatropic/diatropic pattern, whereas the hexaanion has a diatropic/paratropic/diatropic pattern, which is the 'mirror-image' of that of the neutral species. The patterns have been interpreted according to the ipsocentric formulation of the current density. Magnetizability and excitation energy suggest that the hexaanion should be an aromatic molecule. The next homologue of altan-corannulene 6-, altan-altan-corannulene 6-, has also been studied. Its large diamagnetizability has been effectively used to model the magnetic response of C 80 6cages.

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Section: Resultsmentioning

confidence: 91%

Anionic derivatives of altan‐corannulene

Monaco

Zanasi

2013

J of Physical Organic Chem

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“…The geometries were fully optimized at the B3LYP/6-31G(d,p) level of theory. This method and basis set have been widely used in the study of fullerene reactivity [ 30 , 31 ], leading to good agreement with geometrical parameters of fullerene fragments obtained by X-ray diffraction [ 32 ]. The methodology has proven to describe satisfactorily the DA cycloaddition reactions over fullerenes and fullerene fragments [ 33 , 34 ].…”

Section: Methodsmentioning

confidence: 91%

Growth of Fullerene Fragments Using the Diels-Alder Cycloaddition Reaction: First Step towards a C60 Synthesis by Dimerization

Mojica

Méndez²,

Alonso³

2013

Molecules

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Density Functional Theory has been used to model the Diels-Alder reactions of the fullerene fragments triindenetriphenilene and pentacyclopentacorannulene with ethylene and 1,3-butadiene. The purpose is to prove the feasibility of using Diels-Alder cycloaddition reactions to grow fullerene fragments step by step, and to dimerize fullerene fragments, as a way to obtain C60. The dienophile character of the fullerene fragments is dominant, and the reaction of butadiene with pentacyclopentacorannulene is favored.

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“…Based on the satisfactory results delivered by the reaction between 1,3-butadiene and ethylene, we have decided to use the same method to study the Diels-Alder reactions between the substituted hemifullerenes and 1,3-butadiene. This method and basis set have been often used in the study of fullerene reactivity [28,29], leading to good agreement with geometrical parameters of fullerene fragments obtained by X-ray diffraction [30]. The methodology has proven to describe satisfactorily the DA cycloaddition reactions over fullerenes and their fragments [17,31,32].…”

Section: Methodsmentioning

confidence: 99%

The Diels-Alder Cycloaddition Reaction of Substituted Hemifullerenes with 1,3-Butadiene: Effect of Electron-Donating and Electron-Withdrawing Substituents

2016

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Abstract:The Diels-Alder (DA) reaction provides an attractive route to increase the number of six member rings in substituted Polycyclic Aromatic Hydrocarbons (PAHs). The density functional theory (DFT) B3LYP method has been used in this work to inquire if the substitution of H over the edge of triindenetriphenylene (pristine hemifullerene 1) and pentacyclopentacorannulene (pristine hemifullerene 2), could improve the DA cycloaddition reaction with 1,3-butadiene. The substituents tested include electron-donating (NH2, OMe, OH, Me, i-Pr) and electron-withdrawing groups (F, COOH, CF3, CHO, CN, NO2). The electronic, kinetic and thermodynamic parameters of the DA reactions of the substituted hemifullerenes with 1,3-butadiene have been analyzed. The most promising results were obtained for the NO2 substituent; the activation energy barriers for reactions using this substituent were lower than the barriers for the pristine hemifullerenes. This leads us to expect that the cycloadditions to a starting fullerene fragment will be possible.

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Preferential Site of Attack on Fullerene Cations: Frontier Orbitals and Rate Coefficients

Cited by 15 publications

References 18 publications

Anionic derivatives of altan‐corannulene

Anionic derivatives of altan‐corannulene

Growth of Fullerene Fragments Using the Diels-Alder Cycloaddition Reaction: First Step towards a C60 Synthesis by Dimerization

The Diels-Alder Cycloaddition Reaction of Substituted Hemifullerenes with 1,3-Butadiene: Effect of Electron-Donating and Electron-Withdrawing Substituents

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