Heinrich Luftmann

Aza-dihydro[60]fullerene in the gas phase. A mass-spectrometric and quantumchemical study

Abstract A new approach to produce heterofullerenes is described. Starting from a fullerene with an intact cage which is activated by suitable exohedral functionalization, the first aza-heterofullerene is generated in the gas phase under DCI mass-spectrometric conditions. On the basis of AMI-calculations the 1,2-closed structure is proposed to be the most stable one.

Functionalization of [60]fullerene by photoinduced electron transfer (PET): Syntheses of 1-substituted 1,2-dihydro [60]fullerenes

Abstract [60]Fullerene is irradiated in the presence of the electron transfer sensitizer 9,10-dicyanoanthracene (DCA) under cosensitization with biphenyl. The generated radical cation C60•+ reacts with H-donors such as tert-butylmethyl ether, propionaldehyde and alcohols to give 1:1-adducts, the 1-substituted 1,2-dihydro[60]fullerenes.

SYNTHESIS OF 1,2-(2,3-DIHYDRO-1H-AZIRINO)-[60]FULLERENE, THE PARENT FULLEROAZIRIDINE

Abstract The reaction of [60]fullerene with tert -butylazidoformate in 1,1,2,2-tetrachloroethane yields the stable fulleroaziridine 1 . Elimination of the tert -butyloxycarbonyl (BOC) group generates the parent fulleroaziridine C 60 NH 2 .

[60]fullerene radical cation: Reactions and mechanism

Abstract C 60 was irradiated in the presence of several electron transfer photosensitizers. Upon addition of H-donors such as N , N -dimethylformamide, 1,3-dioxolane, phenylacetaldehyde, methyl formate, tert -butanol, propionic acid, glycol and methoxyethanol 1-substituted 1,2-dihydro[60]fullerenes 1–3 and 5–11 and in one case a 1,2,3,4-tetrahydro[60]fullerene, 4 , were formed. A mechanistic pathway involving C 60 •+ is proposed.

Progress in Fullerene Chemistry: From Exohedral Functionalization to Heterofullerenes

Various types of cycloaddition such as [2+1], [2+3], and Diels-Alder reactions have been investigated for the purpose of exohedral functionalization of [60]fullerene and also in few cases of [70]fullerene. Thermal and photochemical activation have been used and lead to a variety of new fullerene derivatives which may be further functionalizable. In addition, a new approach to aza-heterofullerenes has been developed starting from an exohedrally activated fullerene.

Progress in fullerene chemistry: Exohedral functionalization of first and second generation and a new approach to aza-heterofullerenes

Abstract The methodology for exohedral functionalization of fullerenes and their monosubstituted derivatives is discussed (functionalization of first and second generation). Two examples of easily accessible synthetic building blocks are presented, i.e. the cyclohexadione fused [60]fullerene and the aziridino-[60]fullerene. Both are precursors for a variety of higher functionalized fullerene derivatives with interesting properties. In addition, a new approach to azafullerenes in the gas phase is presented starting from an activated monofunctionalized [60]fullerene.