Effect of Xenon on Fullerene Reactions

Frunzi, Michael; Cross, R. J.; Saunders, Martin

doi:10.1021/ja075568n

Cited by 34 publications

(45 citation statements)

References 14 publications

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“…Frunzi, Cross, and Saunders explored experimentally the exohedral reactivity of these single‐Ng compounds. They performed the Diels–Alder reaction between 9,10‐dimethylanthracene (DMA) and 129 Xe@C 60 or 3 He@C 60 to investigate the effect of the trapped noble gas 19. They observed that the thermodynamics of the Diels–Alder reaction was favored at low temperatures in the case of 3 He@C 60 , while at high temperatures the equilibrium constant of the reaction was larger for 129 Xe@C 60 .…”

Section: Introductionmentioning

confidence: 99%

Reactivity and Regioselectivity of Noble Gas Endohedral Fullerenes Ng@C₆₀ and Ng₂@C₆₀ (Ng=He–Xe)

Osuna

Swart

Solà

2009

Chemistry A European J

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Recently, it was shown that genuine Ng-Ng chemical bonds are present in the endohedral fullerenes Ng(2)@C(60) in the case of Ng=Xe, while it is more debatable whether a chemical bond exist for Ng=Ar and Kr. The lighter homologues with helium and neon are weakly bonded van der Waals complexes. The presence of a noble gas dimer inside the cage is expected to modify the exohedral reactivity of the C(60) cage with respect to that of free C(60). To investigate the impact of encapsulated diatomic noble gas molecules on the chemical reactivity of C(60), we analyzed the thermodynamics and the kinetics of [4+2] Diels-Alder cycloaddition of 1,3-cis-butadiene at all nonequivalent bonds in free C(60), Ng@C(60), and Ng(2)@C(60) (Ng=He, Ne, Ar, Kr, and Xe). Our BP86/TZP calculations reveal that introduction of single noble gas atoms in Ng@C(60) and noble gas dimers He(2) and Ne(2) in Ng(2)@C(60) has almost no effect on the exohedral reactivity compared to free C(60), in agreement with experimental results. In all these cases cycloaddition is clearly favored at the [6,6] bonds in the fullerene cage. For the endohedral compounds He(2)@C(60) and Ne(2)@C(60) a slight preference (by less than 2 kcal mol(-1)) for bonds closer to the C(5) symmetry axis is found. This picture changes dramatically for the endohedral compounds with heavier noble gas dimers. Encapsulation of these noble gas dimers clearly enhances the reaction, both under thermodynamic and kinetic control. Moreover, in the case of Xe(2)@C(60), addition to [6,6] and [5,6] bonds becomes equally viable. These reactivity changes in endohedral fullerenes are attributed to stabilization of the LUMO, increased fullerene strain energy, and greater compression of the encapsulated Ng(2) unit along the He to Xe series.

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Section: Introductionmentioning

confidence: 99%

Reactivity and Regioselectivity of Noble Gas Endohedral Fullerenes Ng@C₆₀ and Ng₂@C₆₀ (Ng=He–Xe)

Osuna

Swart

Solà

2009

Chemistry A European J

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“…As a related study, 129 Xe@C 60 was reported to exhibit smaller equilibrium constant in an addition reaction with DMA than that of 3 He@C 60 [78]. The encapsulated 129 Xe atom was suggested to have substantial interaction with C 60 and slightly change the electron distribution of C 60 [78].…”

Section: Diels-alder Reaction Of (H 2 ) 2 @C 70 and H 2 @C 70mentioning

confidence: 79%

“…The encapsulated 129 Xe atom was suggested to have substantial interaction with C 60 and slightly change the electron distribution of C 60 [78]. Theoretical calculations (MPWB1K/6-31G ÃÃ ) [79] of (H 2 ) 2 @C 70 and H 2 @C 70 showed that the longer axis of the C 70 cage of (H 2 ) 2 @C 70 is elongated only by 0.02 A , while the shorter axis is shortened by 0.02 A , as compared to those of H 2 @C 70 .…”

Section: Diels-alder Reaction Of (H 2 ) 2 @C 70 and H 2 @C 70mentioning

confidence: 99%

Molecular Surgery toward Organic Synthesis of Endohedral Fullerenes

Murata

Komatsu

2010

Chemistry of Nanocarbons

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Endohedral fullerenes, the cage-closed carbon molecules that incorporate atom(s) or molecule(s) inside the cage [1-6], are not only of scientific interest but are also expected to be important for their potential use in various fields such as electronics [7], magnetic resonance imaging as a contrast agent [8], and NMR analysis [9, 10]. However, development of their applications has been hampered by a severe limitation in their production, which has relied only on physical methods, such as co-vaporization of carbon and metal atoms [2, 3] and high-pressure/high-temperature treatment with noble gases [9][10][11][12][13], that are difficult to control and yield only milligram quantities of pure product after laborious isolation procedures.Toward the solution of this issue Rubin proposed a concept to realize endohedral fullerenes by the use of organic reactions, that is, 'molecular surgery' [14][15][16]. This approach consists of a series of steps, which are 'incision' of the fullerene cage to form an opening on the surface, insertion of some small atom(s) or molecule(s) through the opening, and 'suture' of the opening to reproduce the fullerene cage while retaining the guest species inside. Toward this purpose, cage-opened C 60 derivative 1 with a 14-membered-ring opening has been synthesized (Figure 8.1) [17], and the insertion of Chemistry of NanocarbonsEdited by Takeshi Akasaka, Fred Wudl and Shigeru Nagase

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“…Recently, the development of the molecular surgery technique has allowed molecules, such as H 2 [12][13][14] and H 2 O [15], to be inserted into fullerene cages. Inside the cages, these molecules are expected to exhibit unusual physical properties that are absent in their isolated form because of the interaction between the encapsulated molecules and the fullerene cages [16,17], as in the case of encapsulated molecules inside carbon nanotubes.…”

Section: Introductionmentioning

confidence: 99%

An anomalous dipole–dipole arrangement of water molecules encapsulated into C60 dimer

Nomura

Okada

2014

Chemical Physics Letters

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a b s t r a c tBased on first-principles total energy calculations, we demonstrate that two water molecules encapsulated in the C 60 dimer form a peculiar tail-to-tail dipole arrangement that is energetically unfavorable in classical electrodynamics. This arrangement is ascribed to charge depression at the wall of C 60 associated with [2 + 2] cycloaddition in the dimer structure resulting in a decrease of the energy cost of Coulomb repulsive interaction in the arrangement. First-principles molecular dynamics simulations also show that the water molecules retain the peculiar arrangement up to the temperature of about 10 K.

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Effect of Xenon on Fullerene Reactions

Cited by 34 publications

References 14 publications

Reactivity and Regioselectivity of Noble Gas Endohedral Fullerenes Ng@C₆₀ and Ng₂@C₆₀ (Ng=He–Xe)

Reactivity and Regioselectivity of Noble Gas Endohedral Fullerenes Ng@C₆₀ and Ng₂@C₆₀ (Ng=He–Xe)

Molecular Surgery toward Organic Synthesis of Endohedral Fullerenes

An anomalous dipole–dipole arrangement of water molecules encapsulated into C60 dimer

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Effect of Xenon on Fullerene Reactions

Cited by 34 publications

References 14 publications

Reactivity and Regioselectivity of Noble Gas Endohedral Fullerenes Ng@C60 and Ng2@C60 (Ng=He–Xe)

Reactivity and Regioselectivity of Noble Gas Endohedral Fullerenes Ng@C60 and Ng2@C60 (Ng=He–Xe)

Molecular Surgery toward Organic Synthesis of Endohedral Fullerenes

An anomalous dipole–dipole arrangement of water molecules encapsulated into C60 dimer

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Product

Resources

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Reactivity and Regioselectivity of Noble Gas Endohedral Fullerenes Ng@C₆₀ and Ng₂@C₆₀ (Ng=He–Xe)

Reactivity and Regioselectivity of Noble Gas Endohedral Fullerenes Ng@C₆₀ and Ng₂@C₆₀ (Ng=He–Xe)