Fullerene Peroxides Research Articles

ChemInform Abstract: Synthesis, Properties and Transformations of Fullerene Peroxides

AbstractReview: 143 refs.

Synthesis of C60(O)3: An Open-Cage Fullerene with a Ketolactone Moiety on the Orifice

Four isomers are currently known for the trioxygenated fullerene derivative C(60)(O)(3), three regioisomers with all of the oxygen addends as epoxy groups and the unstable ozonide isomer with a 1,2,3-trioxlane ring. Here we report the synthesis of an open-cage isomer for C(60)(O)(3) with a ketolactone moiety embedded into the fullerene skeleton through a three-step procedure mediated by fullerene peroxide chemistry. Two fullerene skeleton carbon-carbon bonds are cleaved in the process. The open-cage derivative C(60)(O)(3) can be converted back to C(60) through deoxygenation with PPh(3). Single crystal X-ray structure confirmed the open-cage structure.

Synthesis of fullerene multiadducts with mixed oxygen and nitrogen addends including five secondary amino groups

The reaction of aminoketal[60]fullerene peroxide with pyrrolidine removes all the peroxo groups giving the aminooxahomo[60]fullerene derivatives with five amino addends together with one hydroxyl, one epoxy and three ether moieties. The structure has been determined by spectroscopic data and single crystal X-ray analysis.

Effect of the medium on the reactivity of fullerene N60 with respect to the peroxide radicals RO2 ·. Chemiluminescence in the C60—AIBN—O2—C2H5Ph—PhH system

Chemiluminescence (CL), HLPC, and volumetry were used to demonstrate that fullerene N60 exerts no inhibiting effect on the liquid-phase chain oxidation of hydrocarbons. Peroxide radicals RO2 · do not add to N60 in hydrocarbons with active C—H bond, because the reaction is suppressed by the competing addition of RO2 · to the hydrocarbon. The addition of RO2 · radicals to N60 does occur in benzene (a solvent with strong C—H bonds) in the presence of low concentrations of the hydrocarbon oxidized. Fullerene N60 is found to exhibit a new type of liquid_phase CL, which is presumably generated upon thermal decomposition of fullerene peroxides formed by adding peroxy radicals to fullerene in the C60—AIBN—O2—C2H5Ph—PhH system. The CL spectrum exhibits long-wavelength maxima at 645 and 685 nm. The supposed CL emitters are keto derivatives of fullerene N60.

Synthesis of Fullerene Oxides Containing Both 6,6-Closed Epoxide and 5,6-Open Ether Moieties through Thermolysis of Fullerene Peroxides

Thermolysis of the fullerene hexaadduct C(60)(OO(t)Bu)(6) results in cleavage of two O-O bonds and elimination of two tert-butoxy groups to form two isomeric products with the formula C(60)(O)(2)(OO(t)Bu)(4) in comparable yields. The two oxygen atoms exist as two epoxy groups in one isomer 3, and as an epoxy and an ether group in the other isomer 2. Addition of hydroxylamine to 2 opens both the epoxy and the ether moieties to give a cage-opened keto-ketoxime derivative.

Preparation of fullerenol, fullerenone, and aminofullerene derivatives through selective cleavage of fullerene C–H, C–C, C–N, and C–O bonds in fullerene-mixed peroxide derivatives

Various reactions of fullerene-mixed peroxides were investigated in an effort to explore the chemistry of functional groups on the fullerene surface. Amines convert fullerene peroxides into fullerene epoxides through S N2′ type reaction. Lewis acid catalyzed hydrolysis of fullerene epoxides led to vicinal fullerendiols, which may be oxidized into fullerendiones by diacetoxyiodobenzene (DIB). Alcohols and amines react with the adjacent dione to form acetal or hemiacetal groups through different mechanisms.

Amination of [60]Fullerene by Ammonia and by Primary and Secondary Aliphatic Amines—Preparation of Amino[60]fullerene Peroxides

Ammonia and aliphatic amines react readily in the oxygen-rich regions of the Cs symmetric fullerene peroxides C60(O)(OOtBu)4 (1) and C60(OH)(Br)(OOtBu)4 (2 c). Michael addition-type hydroamination of the 1,4-diene moiety on the central skew-pentagon was observed when 1 was treated with ammonia or with nonbulky primary amines, while sterically demanding primary amines opened the epoxy moiety to form vicinal aminohydroxy fullerene compounds with the amino group on the central pentagon. In 2 c the bromo group was replaced under similar conditions by ammonia and primary amines. Cyclic secondary amines showed different reaction patterns, forming hydrogenation products or aminoketal-fullerenes when treated with 1 and 2 c, respectively. Single-electron transfer (SET) is the key step in all the proposed mechanisms. The compounds were characterized by their spectroscopic data, and in addition, three single-crystal X-ray structures were obtained.

Lewis Acid Promoted Preparation of Isomerically Pure Fullerenols from Fullerene Peroxides C60(OOt‐Bu)6 and C60(O)(OOt‐Bu)6.

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Fullerene Peroxides in Cage‐Opening Reactions

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Fullerene peroxides

t-Butylperoxy radical adds to fullerenes to form a number of stable fullerene mixed peroxides. The reaction follows the stepwise radical addition mechanism, and usually gives a mixture of products with different numbers of t-butylperoxo groups attached on the fullerene cage. Sequential para-addition on the hexagons is the dominant addition pattern. The peroxo groups and fullerene carbons around them exhibit facile reactivity towards various Lewis acids and nucleophiles. The fullerene peroxides can be easily separated by normal column chromatography. Single-crystal X-ray analysis confirmed the presence of peroxo groups. To cite this article L. Gan C.R. Chimie 9 (2006).

Fullerene peroxides in cage-opening reactions

Fullerene-mixed peroxides C60(O)(OOtBu)4 and C60(OOtBu)6 are effective precursors for cage-opened fullerene derivatives. Lewis acids induce the heterolysis of peroxo O-O bond in C60(O)(OOtBu)4. Subsequent Hock-type rearrangement affords both [5,6]- and [6,6]-fullerene hemiketals - oxahomofullerene. Photolysis of C60(OOtBu)6 results in the homolysis of O-O and C-O bonds, affording fullerene diketone as the major product. Spectroscopic data and single-crystal analysis confirmed the cage-opening reactions.