Electrophilic Reactions of C 60 Joe Dunn Miller Group

Introduction Due to the lack in uniformity and solubility of Carbon Nanotubes (CNTs), it is difficult to study their chemistries directly Fullerenes are a very close cousin to Carbon Nanotubes and in most cases they undergo similar chemistries Not only do fullerenes exhibit an increase in solubility as compared to CNTs, but also greater symmetry (I h ).

Introduction (Cont.) C 60 is not known to readily undergo electrophilic addition reactions George A. Olah of the University of Southern California, reported AlCl 3 catalyzed electrophilic addition of benzene and toluene to C 60 in a 1991 JACS article Due to a lack of regioselectivity, the Olah reaction has been largely ignored

Olah’s reactions

Olah’s Proposed Mechanism

Olah’s products 1-2 addition 1-4 addition

Olah’s Evidence NMR Olah also utilized 13 C NMR, IR spectroscopy, and Mass Spec. which revealed evidence of C 60 (C 6 H 6 ) 12 and C 60 (C 6 H 6 ) 16 Toluene reaction

Our Approach (Originally) By using hindered benzene rings, we postulated that we could attain fullerene products with better selectivity (New) Acenes of varying sizes were utilized in an effort to reduce the total number of additions and improve selectivity We also wanted to explore the solid state version of this reaction using a high speed mixing mill, and eventually utilize Microwave Irradiation

Retsh MM 2000 Mixing Mill

Original Reactions Strong mass spec evidence of multiple additions however no insight to mechanism or selective addition was present NMR data was similar however mass spec showed dimerazation of the C60 to C120 Little to no evidence of addition of any kind

New Reactions

58d naphthalene

57f anthracene

Competing Reaction: Diels-Alder

Same Aryl Additions on CNTs

Conclusions & Further Work Each reaction run exhibited potential to have formed the Friedel-Crafts products Further purification is necessary for characterization These reactions can be run in either the solution or solid state Future Work: Isolate products by HPLC Run a mill reaction with 1 molar equivalent of reactant Identify the mechanism in these reactions Publish results