Single and Multiple Additions of Dibenzoylmethane onto Buckminsterfullerene

A novel dibenzoylmethane-fullerene e,e,e-tris adduct was synthesized by the application of a variation of the Bingel–Hirsch conditions and characterized among others by X-ray crystallography. In addition, the corresponding hexakis adduct was detected by MALDI-TOF-MS analysis. Its existence was supported by density-functional-theory (DFT) computations. Furthermore a new synthesis of bis(benzoyl)methanofullerene was established, and its molecular structure was elucidated by X-ray crystallography. DFT computations reproduced the experimentally determined conformation and predict a low energy barrier for the rotation of the two benzoyl moieties.

[1]  A. Hirsch,et al.  Giant fullerene polyelectrolytes composed of C60 building blocks with an octahedral addition pattern and discovery of a new cyclopropanation reaction involving dibromomalonates. , 2013, Chemistry.

[2]  A. Hirsch,et al.  Highly efficient synthesis of globular (bola)amphiphilic [5:1]hexakisadducts of C60. , 2013, Chemistry.

[3]  A. Hirsch,et al.  Efficient synthesis of C2v-symmetrical pentakisadducts of C60 as versatile building blocks for fullerene architectures that involve a mixed octahedral addition pattern. , 2012, Chemistry.

[4]  S. Bräse,et al.  Genetic algorithm density functional theory study of crown ether–dibenzylammonium [2]pseudorotaxanes , 2011 .

[5]  Stefan Bräse,et al.  Di- and dodeca-Mitsunobu reactions on C60 derivatives: post-functionalization of fullerene mono- and hexakis-adducts. , 2009, Chemistry.

[6]  Stefan Bräse,et al.  Functionalization of hexakis methanofullerene malonate crown-ethers: promising octahedral building blocks for molecular networks. , 2009, Chemical communications.

[7]  Ya‐Ping Sun,et al.  Alternatively modified bingel reaction for efficient syntheses of C60 hexakis-adducts. , 2006, Organic letters.

[8]  Zhixin Guo,et al.  Photophysical and Electron-Transfer Properties of Mono- and Multiple-Functionalized Fullerene Derivatives , 2000 .

[9]  Stefan Grimme,et al.  The Addition Patterns of C60 Trisadducts Involving the Positional Relationships e and trans‐n (n = 2–4): Isolation, Properties, and Determination of the Absolute Configuration of Tris(malonates) and Tris[bis(oxazolines)] , 1999 .

[10]  Andreas Hirsch,et al.  Synthesis and Chiroptical Properties of Enantiomerically Pure Bis- and Trisadducts of C60 with an Inherent Chiral Addition Pattern , 1998 .

[11]  A. Hirsch,et al.  Synthesis of [60]fullerene derivatives with an octahedral addition pattern , 1996 .

[12]  A. Hirsch,et al.  Reversible Templataktivierung äquatorialer Doppelbindungen des C60‐Gerüstes: regioselektive Direktsynthese, Struktur und aromatische Eigenschaften von Th‐C66 (COOEt)12 , 1995 .

[13]  A. Hirsch,et al.  [DBU]C60. Spin pairing in a fullerene salt , 1994 .

[14]  Heinrich R. Karfunkel,et al.  Fullerenchemie in drei Dimensionen: Isolierung von sieben regioisomeren Bisaddukten sowie chiralen Trisaddukten aus C60 und Di(ethoxycarbonyl)methylen , 1994 .

[15]  Carsten Bingel,et al.  Cyclopropanierung von Fullerenen , 1993 .

[16]  S. C. O'brien,et al.  C60: Buckminsterfullerene , 1985, Nature.

[17]  C. Barner‐Kowollik,et al.  Well-defined star shaped polymer-fullerene hybrids via click chemistry† , 2009 .

[18]  A. Hirsch,et al.  Efficient cyclopropanation of C60 starting from malonates , 1997 .