PYROLYTIC AND GAS-PHASE FULLERENE DERIVATIZATION REACTIONS

The bulk production of naphthyne derivatives of [60]fullerene, C-60, i s achieved by pyrolysis of 1,8-diiodonaphthalene in the presence of C- 60 Desorption chemical ionization mass spectra, recorded in the negati ve ion mode, show the addition of up to ten naphthyne units to a singl e C-60 molecule. Products containing two C-60 molecules are also gener ated. Tandem mass spectrometry confirms that covalent bonding has occu rred. Similar reactions are described for the reactive intermediates g enerated from 1,8-naphthalic anhydride, 9-iodoanthracene, 2,6-dimethox yiodobenzene, 2-iodonaphthalene and hexabromobenzene. Evidence for a [ 4 + 2] Diels-Alder ion/molecule reaction between mass-selected fullere ne cations and methoxy-substituted 1,3-butadienes is presented. ion/mo lecule reactions of various closed shell cations derived from the diss ociative electron ionization of chlorine containing compounds are show n to result in the methylation, acylation, phenylation and benzylation of fullerenes in the course of positive ion chemical ionization. In t he negative ion mode, halogenated fullerene anions are observed. At hi gh desorption temperatures, the addition of at least 30 hydrogen atoms to C-60 is reported.