Reactions of Anionic Oxygen Nucleophiles with C₆₀Revisited

Abstract

Reactions of C(60) with oxygen nucleophiles of HO(-) and CH(3)O(-) are revisited in PhCN in the presence of PhCH(2)Br. Different from previous results that such reactions lead to the formation of complex mixtures, well-structured C(60) oxazolines are obtained when HO(-) is involved, while di- and tetraadducts with methoxy and benzyl addends are obtained when CH(3)O(-) is engaged. The reactions are followed by in situ vis-near-IR spectroscopy, which reveals further information for the reactions.

Electronic vs Steric Effects on the Stability of Anionic Species: A Case Study on the Ortho and Para Regioisomers of Organofullerenes

“…9 However, no such compound is found from the reaction, indicating that the reaction proceeds via a rather regioselective manner. The result is consistent with the high regioselectivity exhibited by the reactions of anionic oxygen nucleophiles with less symmetrical C 60 derivatives, 7,10 suggesting that the formation of 3 is likely initiated by the nucleophilic addition of MeO − to C 70 at C2, as C2 is the most reactive carbon atom in C 70 due to the largest strain it experiences. 11 The structure of compound 3 is further supported by the spectroscopic characterizations.…”

“…Compounds 1, 2, and 5 were prepared by the reaction of C 60 with MeO − and BnBr following procedures reported previously, and the identity of each compound was confirmed with spectroscopic characterizations by comparing with the reported data. 7 Compounds 3 and 4 were synthesized with procedures similar to those for preparing 1 and 2, except C 70 was used instead of C 60 . Under typical conditions, the yield for 3 and 4 is 34.1% and 2.9%, respectively.…”

“…The bonding of the methoxy group at the C2 atom in both 3 and 4 indicates that the two compounds are likely formed via the same intermediate, 2-MeOC 70 − , followed by the electrophilic addition of the benzyl with either the ortho or the para manner, consistent with the mechanism for formation of C 60 analogues 1 and 2. 7 Electrochemical Study of Compounds 1−4. Compound 1 exhibits three quasireversible one-electron transfer processes with E 1/2 at −1.04, −1.45, and −2.00 V vs ferrocene/ferrocenium (Fc/Fc + , the E 1/2 for the Fc/Fc + redox couple is measured to be at 0.50 V vs SCE under experimental conditions, Figure S11, Supporting Information), indicating that the anionic species of 1 are stable.…”

Hydration or hydroxylation: direct synthesis of fullerenol from pristine fullerene [C60] via acoustic cavitation in the presence of hydrogen peroxide

“…cOH radicals as reactive oxygen species (ROS) attach onto the C 60 cage to give fullerenol (Path I), and/or -OH and cOOH radicals attack the electron decient C 60 double bonds in a nucleophilic reaction and this leads to the formation of fullerene epoxide [C 60 O n ] as an intermediate in the rst stage (Path II) which is similar to the mechanism of the Bingel reaction. 37,57 Further, the repeated attack of cOH (or cOOH) on C 60 O via an S N 2 reaction results in polyhydroxylated fullerene or fullerenol.…”

Vis-Near-IR Spectroscopic and Time-Dependent DFT Study of Reduced Singly Bonded C60 Species

“…26,32,34 Compound 2b was obtained with procedures similar to that for producing 2a. 26 Typically, 50 mg of C 60 (69 μmol) was put into 30 mL of an o-methylbenzonitrile/ODCB (o-dichlorobenzene) mixture (1:1 v/v). The mixture was kept stirring under argon for 10 min, and then 152 μL of TBAOH (1.0 M in methanol, 152 μmol, 2.2 equiv to C 60 ) was added into the solution.…”