Gas-phase reactions of the buckminsterfullerene cations C60.bul.+, C602+, and C60.bul.3+ with water, alcohols, and ethers

Abstract

The reactions of the fullerene ions C[sub 60][sup [center dot]+], C[sub 60][sup 2+], and C[sub 60][sup [center dot]3+] with the neutrals H[sub 2]O, CH[sub 3]OH, CH[sub 3]CH[sup 2]OH, CH[sub 3]CH[sub 2]CH[sub 2]OH, (CH[sub 3])$[sub 2]CHOH, CH[sub 3]OCH[sub 3], (CH[sub 3]CH[sub 2])[sub 2]O, and c-C[sub 4]H[sub 8]O in helium at 0.35 [+-] 0.01 Torr and 294 [+-] 2 K have been studied using a selected-ion flow tube. Association was the most commonly encountered primary product channel seen in the reactions of C[sub 60][sup 2+]: in keeping with earlier studies, there was a clear dependence of the efficiency of association (and of reactivity in general) upon the size of the neutral. Other product channels evident in the reactions of the dication were charge transfer (the major product channel seen in the reaction with diethyl ether) and hydroxide abstraction to form the ion C[sub 60]OH[sup +] (in the reactions with ethanol and 2-propanol). Charge transfer and hydroxide abstraction were seen in several reactions of the trication, C[sub 60][sup [center dot]3+]: association was observed as a minor channel in the reactions with methanol, ethanol, and 1-propanol. A clear difference was observed in the reactivity of the polycationic adducts of alcohols and ethers: alcohol adductsmore » were observed to react further by efficient proton transfer to the parent alcohol, whereas the adducts of ethers did not display subsequent proton transfer to the parent ether. 49 refs., 5 figs., 2 tabs.« less