Reversible and Regioselective Reaction of La@C<sub>82</sub>with Cyclopentadiene

Maeda, Yutaka; Miyashita, Jun; Hasegawa, Tadashi; Wakahara, Takatsugu; Tsuchiya, Takahiro; Nakahodo, Tsukasa; Akasaka, Takeshi; Mizorogi, Naomi; Kobayashi, Kaoru; Nagase, Shigeru; Kato, Tatsuhisa; Ban, Noritaka; Nakajima, Hiroshi; Watanabe, Yoshihito

doi:10.1021/ja053983e

Cited by 60 publications

(53 citation statements)

References 27 publications

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“…[43] Those derivatives were analyzed by HPLC and mass spectrometry, but the regiochemistry of the bisadducts was not described. Also in the same year Akasaka, Nagase, and co-workers [46] reported the reversible and regioselective addition reaction of La@C 82 (C 2v ; 1 a) with cyclopentadiene (Cp, 9), whereby Cp was added in excess to a degassed solution of 1 a in toluene (Scheme 4). The reaction was monitored by EPR over two hours in the dark.…”

Section: [4+2] Cycloadditions: Diels-alder Reactionsmentioning

confidence: 99%

“…Furthermore, the retroDiels-Alder reaction was obtained at 298 K in toluene, with an activation energy even lower than that of the retro reaction of C 60 Cp. [46] Dorn and co-workers took advantage of the higher reactivity of empty fullerenes and classical EMFs compared to metallic nitride EMFs towards Diels-Alder reactions for the purification of metallic nitride EMFs from the extracted fullerenes.…”

Section: [4+2] Cycloadditions: Diels-alder Reactionsmentioning

confidence: 99%

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Chemical, Electrochemical, and Structural Properties of Endohedral Metallofullerenes

et al. 2009

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Ever since the first experimental evidence of the existence of endohedral metallofullerenes (EMFs) was obtained, the search for carbon cages with encapsulated metals and small molecules has become a very active field of research. EMFs exhibit unique electronic and structural features, with potential applications in many fields. Furthermore, functionalized EMFs offer additional potential applications because of their higher solubility and their ease of characterization by X-ray crystallography and other techniques. Herein we review the general field of EMFs, particularly of functionalized EMFs. We also address their structures and their (electrochemical) properties, as well as applications of these fascinating compounds.

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Section: [4+2] Cycloadditions: Diels-alder Reactionsmentioning

confidence: 99%

Section: [4+2] Cycloadditions: Diels-alder Reactionsmentioning

confidence: 99%

Chemical, Electrochemical, and Structural Properties of Endohedral Metallofullerenes

et al. 2009

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“…Metallofullerenes (MFs) have been used with many organic reactions including as: [1 + 2] cycloadditions, 33 [3+2] cycloadditions, 34,35 Prato reactions, 33,36,37 and Diels-Alder type cycloadditions. 34,38 Cui et al 38 documented the nature of an encapsulated metal cation for the regioselectivity and the reactivity in the Diels-Alder (DA) cycloaddition of cyclopentadiene (CpH) to M + @C 60 (M = Li, Na, K, Rb, and Cs) and Ca 2+ @C 60 by density functional theory in the gas phase and solvents. It was shown that metal cations could promote the reactions of CpH and C 60 because they decrease the activation barriers and make the reactions more exothermic and exergonic, or less endothermic and endergonic.…”

Section: Fullerene Derivatives: the Race To Characterizementioning

confidence: 99%

Review—The Beautiful Molecule: 30 Years of C₆₀and Its Derivatives

Acquah

Penkova

Markelov

et al. 2017

ECS J. Solid State Sci. Technol.

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In 1996 Sir Harold W. Kroto, Robert F. Curl and Richard E. Smalley were honored with the Nobel Prize in Chemistry for the discovery of fullerenes. The advent of these new forms of carbon heralded a race to understand the physical and chemical properties. C 60 is virtually insoluble in polar solvents but is partially soluble in benzene, toluene, and carbon disulfide. This made the processing of fullerenes for new applications fairly problematic. However, the physical and chemical properties of these cage structures may be tailored for a wide range of applications. Some of the difficulties in processing have been overcome by using novel fullerene derivatives. The functionalization of the fullerene core with different chemical moieties provided a vector toward potential applications in drug delivery, optoelectronics, electrochemistry and organic photovoltaics. In this review, we will take a closer look at the features of some of the fullerene derivatives that have reinvigorated the field of fullerene research. Water-soluble polyhydroxylated fullerenes such as fullerenol have demonstrated the potential for good electron transfer and optical transmission, while hydrophobic fullerene derivatives have shown promising avenues for catalytic applications. 2015 marked the 30 th anniversary of the discovery of fullerenes, with celebrations around the world including an event by the Royal Society of Chemistry, bringing together many of Sir Harold Kroto's former students. The event also coincided with the recent discovery of C 60 + in space after a complex twenty-year search. It is with sadness that we, Harry's Research Group at Florida State University, and his international collaborators, reflect on the passing of Sir Harold Kroto. His dedication to science and commitment to science communication through the VEGA Science Trust and the Global Educational Outreach for Science Engineering and Technology (GEOSET) initiative help to raise awareness of the challenges for science in the modern world. We will continue to inspire young students through outreach activities he initiated. Nanostructured carbon materials including fullerenes, carbon nanotubes, graphene and carbon black have the potential to be transformative in many areas from medicine to engineering. Research into carbon nanotubes is diverse in areas such as electrochemical devices, field emission, sensors and probes. [1][2][3][4] Recently, carbon nanotubes have been used as additives in the thermoplastics typically used for 3D printing. 5,6 Graphene is the latest material to have peaked interest in the carbon field in a similar manner to carbon nanotubes, with a range of potential applications.7 Graphene oxide is being explored in the production of 3D holographic images. 8The famous paper in Nature, C60:Buckminsterfullerene, 9 introduced the world to the new form of carbon but the road to general acceptance at that time was difficult, even with mounting evidence in support of the discovery. The paper, now cited over 10,000 times has become the central point of referen...

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“…116 DielsAlder (DA) reaction of La@C 2v (9)-C 82 with cyclopentadiene (Cp) proceeded smoothly to afford a single product. 117 The high regioselectivity is noteworthy because 24 nonequivalent carbons and 19 nonequivalent 6,6-ring junctions are on the C 2v (9)-C 82 cage. However, the thermal instability of the product hampered the determination of the molecular structure.…”

Section: Sbclmentioning

confidence: 99%

Emergence of Highly Elaborated π-Space and Extending Its Functionality Based on Nanocarbons: New Vistas in the Fullerene World

Yamada

Akasaka

2014

Bulletin of the Chemical Society of Japan

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How the electronic properties and chemical reactivity of empty fullerenes can be changed upon endohedral metaldoping? How the dynamic behavior and position of encapsulated metal atoms can be controlled? How its functionality can be extended by chemical treatments? We have addressed all aspects of endohedral metallofullerenes, including the synthesis, isolation, structure, chemical properties, and theoretical considerations and their applications in the related fields to answer these questions.

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Reversible and Regioselective Reaction of La@C₈₂with Cyclopentadiene

Abstract: The reversible and regioselective reaction of La@C82 with cyclopentadiene was carried out. The activation and thermodynamic parameter of the retro-reaction was estimated from the Arrhenius plots of the rate constants.

Cited by 60 publications

References 27 publications

Chemical, Electrochemical, and Structural Properties of Endohedral Metallofullerenes

Chemical, Electrochemical, and Structural Properties of Endohedral Metallofullerenes

Review—The Beautiful Molecule: 30 Years of C₆₀and Its Derivatives

Emergence of Highly Elaborated π-Space and Extending Its Functionality Based on Nanocarbons: New Vistas in the Fullerene World

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Reversible and Regioselective Reaction of La@C82with Cyclopentadiene

Abstract: The reversible and regioselective reaction of La@C82 with cyclopentadiene was carried out. The activation and thermodynamic parameter of the retro-reaction was estimated from the Arrhenius plots of the rate constants.

Cited by 60 publications

References 27 publications

Chemical, Electrochemical, and Structural Properties of Endohedral Metallofullerenes

Chemical, Electrochemical, and Structural Properties of Endohedral Metallofullerenes

Review—The Beautiful Molecule: 30 Years of C60and Its Derivatives

Emergence of Highly Elaborated π-Space and Extending Its Functionality Based on Nanocarbons: New Vistas in the Fullerene World

Contact Info

Product

Resources

About

Reversible and Regioselective Reaction of La@C₈₂with Cyclopentadiene

Review—The Beautiful Molecule: 30 Years of C₆₀and Its Derivatives