Application of Solid-State and High-Pressure Reactions for Fullerene Derivatization and CO2 Activation (ORGANIC MATERIALS CHEMISTRY-High-Pressure Organic Chemistry)

Abstract

Under the solid-state reaction conditions, a nucleophilic addition of organozinc reagent occurs on fullerene C60 to give a monoadduct together with a bisadduct and a cyclopropanofullerene. Surprisingly, the fullerene C60 also undergoes a clean [2+2] type dimerization by the action of KCN or Mg powder under the similar reaction conditions. The fullerene dimer thus obtained is the very first example of (C60)2, and its structure has been determined by the X-ray crystallography. The use of high pressure (5000 atm) was also shown to be advantageous for a liquid-phase [4+2] cycloaddition of C60. The high-pressure reaction of CO with supercritical CO2 has been found to effect the C-C bond formation affording an oxalate salt in good yield in the presence of Cs2CO3.