Some inorganic chemistry of the new carbon cage cluster, Buckminsterfullerene, C₆₀
Chapter 1 reviews the relevant and particularly interesting chemistry of C60 and includes some chemical aspects of the other recently discovered new forms of carbon including the graphitic carbon nanotubules, concentric carbon spheres and amorphous carbon networks. An experimental section describes the techniques used for the synthesis of fullerene rich soot and the subsequent isolation and purification of C60 as performed in the Inorganic Chemistry Laboratory, Oxford. Chapter 2 describes the synthesis, characterisation, and some reaction chemistry of the new complex Rh(η2-C60)(CO)(H)(PPh3)2 and its activity with respect to the catalytic hydroformylation of ethene and propene, and is compared to the industrially used catalyst Rh(CO)(H)(PPh3)3. Studies to determine the thermal stability of Rh(η2-C60)(CO)(H)(PPh3)2 compared to Rh(CO)(H)(PPh3)3 during hydroformylation catalysis are also included. Chapter 3 describes the synthesis and characterisation of the new complexes NaC60.5thf, NMe4C60.1.5thf and what could be the new complex Na0.9C60.3thf. These materials exhibit a magnetic transition at approximately 180K as determined by bulk static D.C. susceptibility measurements and electron spin resonance spectroscopy. This transition is discussed mainly in terms of a metal-metal or metal-insulator transition. Some reaction chemistry of these materials is also described. Also described are studies into various aspects of the sodium C60 phase diagram at ambient temperature and pressure with regard to the proposed solid solution behaviour in the compositional range Na1C60 to Na3C60. The synthesis of the novel hexagonal close packed compounds Na6C60 and Na9C60 and consequences for the phase diagram of sodium C60 intercalates are discussed. Chapter 4 describes the synthesis of various alkali metal C60 intercalates using a microwave induced argon plasma as the heat source. The developement of this technique for the bulk synthesis of other materials and attempts at the synthesis of novel lithium and ytterbium intercalates are also described.