Formation of C60 adducts with two different alkyl groups via combination of electron transfer and S(N)2 reactions

Shunichi Fukuzumi, Tomoyoshi Suenobu, Takeomi Hirasaka, Ryuichi Arakawa, Karl M. Kadish

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127 Scopus citations

Abstract

The formation of organofullerenes of the type R2C60 and R(R')C60 from C602- and alkyl halides (RX or R'X) in benzonitrile was mechanistically investigated for 15 different alkyl halides which vary in electrophilicity and electron acceptor ability. The first step in the reaction leads to RC60- via an electron-transfer mechanism, followed by formation of R2C60 or R(R')C60 via an S(N)2 mechanism. Evidence of the mechanism comes from comparison of rate constants for the stepwise addition of two R groups to C602- with rate constants for the genuine electron transfer and S(N)2 reactions. The formation of t-BuC60- and PhCH2C60- after the first R group addition was confirmed by electrospray ionization mass spectroscopy. The t-BuC60-derivative will not react further with excess t-BuI, but this is not the case for the less sterically hindered PhCH2Br, which adds to t-BuC60- in benzonitrile to give t- Bu(PhCH2)C60. A protonation of t-BuC60- with trifluoroacetic acid can also occur to give 1,4-t-Bu(H)C60, which rearranges rapidly to yield 1,2- t-Bu(H)C60. Rate constants for the second alkylation of t-BuC60- with a variety of different alkyl halides are compared with values of genuine S(N)2 reactions and indicate that the second step in the fullerene alkylation reaction proceeds via an S(N)2 mechanism. The rate constants of electron transfer from C602- to RX span a range of 105, but are insensitive to the steric effect of the alkyl group, i.e., they depend only on the electron- acceptor ability of RX. In contrast, the S(N)2 rate constants of t-BuC60- with RX are highly susceptible to the steric effect of the alkyl group and no reaction at all takes place between t-BuC60- and t-BuI. Thus, the first addition of one sterically hindered alkyl group to C602- occurs via electron transfer and cannot be followed by further addition of a second sterically hindered group (via an S(N)2 reaction). This is not the case for less sterically hindered alkyl groups such as benzyl bromide which can add via an S(N)2 reaction to yield C60 adducts with two different alkyl groups.

Original languageEnglish
Pages (from-to)9220-9227
Number of pages8
JournalJournal of the American Chemical Society
Volume120
Issue number36
DOIs
StatePublished - 16 Sep 1998

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