GAS-PHASE REACTIONS OF THE BUCKMINSTERFULLERENE CATIONS C-60(.-60(2+), AND C-60(.3+) WITH WATER, ALCOHOLS, AND ETHERS(), C)

Citation
G. Javahery et al., GAS-PHASE REACTIONS OF THE BUCKMINSTERFULLERENE CATIONS C-60(.-60(2+), AND C-60(.3+) WITH WATER, ALCOHOLS, AND ETHERS(), C), Journal of the American Chemical Society, 115(14), 1993, pp. 6295-6301
Citations number
54
Categorie Soggetti
Chemistry
ISSN journal
00027863
Volume
115
Issue
14
Year of publication
1993
Pages
6295 - 6301
Database
ISI
SICI code
0002-7863(1993)115:14<6295:GROTBC>2.0.ZU;2-G
Abstract
The reactions of the fullerene ions C60.+, C60(2+), and C-60(.3+) with the neutrals H2O, CH3OH, CH3CH2OH, CH3CH2CH2OH, (CH3)2CHOH, CH3OCH3, (CH3CH2)2O, and c-C4H8O in helium at 0.35 +/- 0.01 Torr and 294 +/- 2 K have been studied using a selected-ion flow tube. Association was th e most commonly encountered primary product channel seen in the reacti ons of C60(2+): in keeping with earlier studies, there was a clear dep endence 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 chan nel seen in the reaction with diethyl ether) and hydroxide abstraction to form the ion C60OH+ (in the reactions with ethanol and 2-propanol) . Charge transfer and hydroxide abstraction were seen in several react ions of the trication, C-60(.3+): association was observed as a minor channel in the reactions with methanol, ethanol, and 1 -propanol. A cl ear difference was observed in the reactivity of the polycationic addu cts of alcohols and ethers: alcohol adducts were observed to react fur ther by efficient proton transfer to the parent alcohol, whereas the a dducts of ethers did not display subsequent proton transfer to the par ent ether. This difference in reactivity is interpreted in terms of th e difference in ease of proton loss from the structures ascribed to th e fullerene polycation adducts of alcohols and ethers. The monocation C60.+ was unreactive with all of the species studied here: monocationi c product ions (C60OH+, C60OR+) were also observed to be unreactive wi th the neutrals from which they were produced. The implications of the non-reactivity of C60.+ and the reactivity of C-60(2+) for the chemic al evolution of interstellar clouds and circumstellar shells are brief ly discussed.