Synthesis and regiochemistry of [60]fullerenyl 2-methylmalonate bisadducts and their facile electron-accepting properties.
A simple one-pot reaction using in situ chemically generated Na-naphthalenide as an electron reductant in the preferential generation of C(60)(2-) is described. Trapping of C(60)(2-) intermediate with 2 molar equiv of sterically hindered 2-bromo-2-methylmalonate ester afforded two singly bonded fullerenyl bisadducts C(60)[-CMe(CO(2)Et)(2)](2) in 35% and 7% yield, respectively. The regiochemistry of these two products was determined to be 1,4- and 1,16-bisadducts, respectively, by NMR, UV-vis-NIR, LCMS, and X-ray single crystal structural analysis. The minor 1,16-bisadduct 2 exhibits long wavelength absorption bands in the near-IR region and prominent electron-accepting characteristics as compared with those of the major 1,4-bisadduct and pristine C(60). As revealed by DFT calculation, we propose that the origin of these unusual characters of 2 arises from the moiety of [18pi]-trannulene, in close resemblance to that of the highly symmetrical emerald green 1,16,29,38,43,60-hexaadduct of C(60), EF-6MC(n). Accordingly, we anticipate a fast progressive formation of plausible 1,16-bisadduct-like intermediate moieties on a C(60) cage as the precursor structure leading to the formation of EF-6MC(n), by taking the corresponding regiochemistry and electronic properties into account.
Kokubo
Ken
K
Division of Applied Chemistry, Graduate School of Engineering, Osaka University, Osaka 565-0871, Japan. kokubo@chem.eng.osaka-u.ac.jp
Arastoo
Riyah S
RS
Oshima
Takumi
T
Wang
Chun-Chih
CC
Gao
Yuan
Y
Wang
Hsing-Lin
HL
Geng
Hao
H
Chiang
Long Y
LY
D003500:Cyclization; D004563:Electrochemistry; D004583:Electrons; D037741:Fullerenes / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008314:Malonates / Q000138:chemical synthesis* / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D013237:Stereoisomerism
D037741:Fullerenes; D008314:Malonates; C530172:pristine (C60); C030290:malonic acid