Synthesis of an Azahomoazafullerene C₅₉N(NH)R and Gas‐Phase Formation of the Diazafullerene C₅₈N₂

Punching a Carbon Atom of C60 into its Own Cavity to Form an Endohedral Complex CO@C59O6 under Mild Conditions

“…Fullerene‐bound hydroxylamino group is prone to rearrangement as shown in our previous studies 11. 14, 21 To expand the orifice we treated compound 4 with diacetoxyl iodobenzene (DIB). To our surprise, compound 5 with a CO molecule trapped in the cavity was isolated.…”

Redox‐Dependent Transformation of a Hydrazinobuckybowl between Curved and Planar Geometries

“…[5] Compounds 1 are the first hydrazine-embedded buckybowls with the diindenochrysene [6] skeleton 2 and ap artial structure of the unidentified hydrazine-embedded fullerene C 58 N 2 . [7] We succeeded in synthesizing 1avia the strained cyclobicarbazole 3a,w hich was obtained by the reductive desulfurization of ap henothiazine to form ac arbazole skeleton. Owing to the hydrazine-embedded polyarene structure, [8] the stable monocation and dication were generated by stepwise two-electron oxidation.…”

Fullerene‐Based Macro‐Heterocycle Prepared through Selective Incorporation of Three N and Two O Atoms into C60

“…Compound 6 with three 4-methylpiperidinyl groups was obtained as the major product. Thee namine double bond in 1 is an active anti-Bret double bond, which is prone to further addition either in the 1,2-addition pattern for sterically less hindered addends such as methanol [11] or the 1,4-addition pattern for bulky addends as in the present case.S toichiometrically two hydrogen atoms from the two 4-methylpiperidine converted a t-butylperoxo group into t-butanol and the hydroxy group in 6.There is no hemiaminal moiety in 6.Sothe local ring strain in 3 is akey driving force for the opening of the cage to form the hetero-macrocycle.T he structure of 6 was confirmed by…”

“…Compound 1 [11] was previously prepared as aprecursor to the diazafullerene C 58 N 2 , [12] which was detected in the gas phase by MALDI-TOF mass spectrometry.T he key step for the introduction of the two nitrogen atoms on the cage skeleton to give 1 is the addition of hydroxylamine and subsequent PCl 5 -induced rearrangement processes.T oi ntroduce another nitrogen atom, we replaced the chlorine atom with hydroxylamine to form compound 2 (Scheme 1). The4bromoaniline and naphthalene-2-amine both with aN H 2 group also reacted with 1 to form analogous compounds 2b and 2c,r espectively.A se xpected, treatment of the hydroxylamino derivative 2a with PCl 5 resulted in insertion of the nitrogen atom into af ullerene C À Cb ond to form the C s symmetric compound 3.U nlike the chlorine atom in compound 1, the chlorine atom in 3 could not be replaced by hydroxylamine or other primary amines,such as aniline.…”