Reductive Hydrogenation of Cs -C70 (CF3 )8 and C1 -C70 (CF3 )10

Victor A Brotsman; Viktor P Bogdanov; Alexey V Rybalchenko; Evgenia P Galanicheva; Nikita M Belov; Vitaliy Yu Markov; Natalia S Lukonina; Ilya N Ioffe; Sergey I Troyanov; Erhard Kemnitz; Alexey A Goryunkov

doi:10.1002/asia.201600491

Reductive Hydrogenation of Cs -C70 (CF3 )8 and C1 -C70 (CF3 )10

Chem Asian J. 2016 Jul 5;11(13):1945-54. doi: 10.1002/asia.201600491. Epub 2016 Jun 6.

Affiliations

¹ Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia.
² Institute of Chemistry, Humboldt University Berlin, Brook-Taylor-Strasse 2, 12489, Berlin, Germany.
³ Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia. aag@thermo.chem.msu.ru.

PMID: 27159775
DOI: 10.1002/asia.201600491

Abstract

CF3 -derivatized fullerenes prove once again to be promising scaffolds for regioselective fullerene functionalization: now with the smallest possible addends-hydrogen atoms. Hydrogenation of Cs -C70 (CF3 )8 and C1 -C70 (CF3 )10 by means of reduction with Zn/Cu couple in the presence of water proceeds regioselectively, yielding only one major isomer of C70 (CF3 )8 H2 and only two for C70 (CF3 )10 H2 , whose addition patterns are combined in the only abundant isomer of C70 (CF3 )10 H4 . The observed selectivity is governed by the electronic structure of trifluoromethylated substrates. Interestingly, we discovered that Clar's theory can be utilized to predict the regiochemistry of functionalization, and we look forward to testing it on forthcoming cases of derivatization of pre-functionalized fullerene building blocks.

Keywords: Clar's sextets rule; fullerenes; hydrogenation; regioselectivity; structure elucidation.