TY - JOUR
T1 - Pyrolytic and gas phase fullerene derivatization reactions
AU - Hoke, Steven H.
AU - Molstad, Jay
AU - Kahr, Bart
AU - Cooks, R. Graham
N1 - Funding Information:
S.H.H. acknowledges BASF Corporation for fellowship support. J.C.M. acknowledges a Quest Fellowship and an Eli Lilly and Company Scholarship. This work was supported by the National Science Foundation, CHE 92-23791.
PY - 1994/10/13
Y1 - 1994/10/13
N2 - The bulk production of naphthyne derivatives of [60]fullerene, C60, is achieved by pyrolysis of 1,8-diiodonaphthalene in the presence of C60. Desorption chemical ionization mass spectra, recorded in the negative ion mode, show the addition of up to ten naphthyne units to a single C60 molecule. Products containing two C60 molecules are also generated. Tandem mass spectrometry confirms that covalent bonding has occurred. Similar reactions are described for the reactive intermediates generated from 1,8-naphthalic anhydride, 9-iodoanthracene, 2,6-dimethoxyiodobenzene, 2-iodonaphthalene and hexabromobenzene. Evidence for a [4 + 2] Diels-Alder ion/molecule reaction between mass-selected fullerene cations and methoxy-substituted 1,3-butadienes is presented. Ion/molecule reactions of various closed shell cations derived from the dissociative electron ionization of chlorine containing compounds are shown to result in the methylation, acylation, phenylation and benzylation of fullerenes in the course of positive ion chemical ionization. In the negative ion mode, halogenated fullerene anions are observed. At high desorption temperatures, the addition of at least 30 hydrogen atoms to C60 is reported.
AB - The bulk production of naphthyne derivatives of [60]fullerene, C60, is achieved by pyrolysis of 1,8-diiodonaphthalene in the presence of C60. Desorption chemical ionization mass spectra, recorded in the negative ion mode, show the addition of up to ten naphthyne units to a single C60 molecule. Products containing two C60 molecules are also generated. Tandem mass spectrometry confirms that covalent bonding has occurred. Similar reactions are described for the reactive intermediates generated from 1,8-naphthalic anhydride, 9-iodoanthracene, 2,6-dimethoxyiodobenzene, 2-iodonaphthalene and hexabromobenzene. Evidence for a [4 + 2] Diels-Alder ion/molecule reaction between mass-selected fullerene cations and methoxy-substituted 1,3-butadienes is presented. Ion/molecule reactions of various closed shell cations derived from the dissociative electron ionization of chlorine containing compounds are shown to result in the methylation, acylation, phenylation and benzylation of fullerenes in the course of positive ion chemical ionization. In the negative ion mode, halogenated fullerene anions are observed. At high desorption temperatures, the addition of at least 30 hydrogen atoms to C60 is reported.
KW - Chemical ionization
KW - Cycloaddition
KW - Fullerenes
KW - Pyrolytic reaction
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U2 - 10.1016/0168-1176(94)04038-9
DO - 10.1016/0168-1176(94)04038-9
M3 - Article
AN - SCOPUS:0005183065
SN - 0168-1176
VL - 138
SP - 209
EP - 219
JO - International Journal of Mass Spectrometry and Ion Processes
JF - International Journal of Mass Spectrometry and Ion Processes
IS - C
ER -