Chemical generation of C602- and electron transfer mechanism for the reactions with alkyl bromides

Ramakrishnan Subramanian, Karl M. Kadish, Madakasira N. Vijayashree, Xiang Gao, M. Thomas Jones, Mitchell D. Miller, Kurt L. Krause, Tomoyoshi Suenobu, Shunichi Fukuzumi

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103 Scopus citations


A simple solution-phase method that uses chemically generated p-benzoquinone dianions (Q2-) as the reductant in the selective generation of either C60•- or C602- is described. The electron transfer reduction of C60 by Q2- occurs via stepwise electron transfer from the Q2- to C60 in acetonitrile or benzonitrile. The C602- thus generated is used as the starting material in the synthesis of RxC60 (where x = 2 for R = C6H5CH2 and x = 1 for R = o-xylyl) by the reaction of C602- with benzyl bromide or α,α′-dibromo-o-xylene. Theoretical calculations predict that the 1,4-isomer of (C6H5CH2)2C60 should be selectively formed, and this is confirmed by single-crystal X-ray diffraction studies. UV-visible and near-IR spectroscopy were used to monitor the progress of electron transfer from the Q2- to C60 as well as the subsequent reactions between C602- and the alkyl bromides. The comparison of the observed rate constants of the reactions of C602- with those of electron transfer from tetramethylsemiquinone radical anion to the same alkyl bromide indicates that the formation of RxC60 proceeds via the rate-determining electron transfer from C602- to the alkyl bromide.

Original languageEnglish
Pages (from-to)16327-16335
Number of pages9
JournalJournal of Physical Chemistry
Issue number40
StatePublished - 3 Oct 1996


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