Manganese(iii) acetate-mediated activation of C-H bonds of weak CH-acids; addition of o-carborane, its derivatives, and some other CH-acids to [60]-fullerene

Boris L Tumanskii; Denis S Sabirov; Stanislav P Solodovnikov; Yury I Lyakhovetsky

doi:10.1039/c8dt04565h

Manganese(iii) acetate-mediated activation of C-H bonds of weak CH-acids; addition of o-carborane, its derivatives, and some other CH-acids to [60]-fullerene

Dalton Trans. 2019 Feb 5;48(6):2046-2058. doi: 10.1039/c8dt04565h.

Authors

Boris L Tumanskii¹, Denis S Sabirov, Stanislav P Solodovnikov, Yury I Lyakhovetsky

Affiliation

¹ A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 28 Vavilov St., 119991 GSP-1 Moscow V-334, Russia. yulyakh@ineos.ac.ru.

PMID: 30656312
DOI: 10.1039/c8dt04565h

Abstract

o-Carborane, 9-I-o-carborane, 1-Me-o-carborane, and several other CH-acids, 9H-fluorene, 2-Br-9H-fluorene, and trimethylsylylacetylene, have been shown to react with C60 affording their monoadducts with fullerene, the reaction being mediated by Mn(OAc)3·2H2O. In the case of o-carborane, when the molar ratio of C60 : o-carborane : Mn(OAc)3·2H2O was 1 : 21 : 20, polyaddition occurred to furnish adducts bearing between one and six o-C2HB10H10 groups. A distinguishing characteristic of the carboranyl derivatives of C60 obtained appeared to be that the carboranyl moieties were connected to the fullerenyl one by their carbon atom. No such fullerene derivatives have been known so far. Based on the results previously obtained for the phosphonylation of fullerenes, an oxidative-ion-transfer (OIT) mechanism was suggested for the reactions. The mechanism involves the replacement of an acetate group in Mn(OAc)3 with the corresponding R of a CH-acid (RH), oxidation of C60 by Mn(OAc)2R with the formation of a pair [C60˙+, Mn(OAc)2R˙-] followed by the transfer of R- to C60˙+ to furnish the radical RC60˙. The radical abstracts a hydrogen atom from another molecule of RH or from the solvent. The polyaddition occurs in an analogous way. This mechanism found support in this study owing to the fact that the reactions of both o-carborane and 9H-fluorene did not proceed with perfluorobenzophenone as a substrate, because it was unable to undergo oxidation. C70 reacted with o-carborane in a similar way to give the corresponding monoadduct. No reaction of C60 with m-carborane was observed and this was explained by its insufficient CH-acidity.