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Synthesis and Regiochemistry of [60]Fullerenyl 2-Methylmalonate Bisadducts and their Facile Electron-Accepting Properties
- Publication Year :
- 2010
-
Abstract
- 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.
- Subjects :
- chemistry.chemical_classification
Steric effects
Models, Molecular
Magnetic Resonance Spectroscopy
Molecular Structure
Chemistry
Stereochemistry
Organic Chemistry
Regioselectivity
Electrons
Stereoisomerism
Nuclear magnetic resonance spectroscopy
Crystal structure
Electron acceptor
Article
Malonates
Crystallography
Cyclization
Electrochemistry
Moiety
Molecule
Fullerenes
Single crystal
Subjects
Details
- Language :
- English
- Database :
- OpenAIRE
- Accession number :
- edsair.doi.dedup.....c113a9ca3389b27117d2b3987220bc1c