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Hydrocarbon-soluble, hexaanionic fulleride complexes of magnesium

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Abstract

The reaction of the magnesium(I) complexes [{(Arnacnac)Mg}2], (Arnacnac = HC(MeCNAr)2, Ar = Dip (2,6-iPr2C6H3), Dep (2,6-Et2C6H3), Mes (2,4,6-Me3C6H2), Xyl (2,6-Me2C6H3)) with fullerene C60 afforded a series of hydrocarbon-soluble fulleride complexes [{(Arnacnac)Mg}nC60], predominantly with n = 6, 4 and 2. 13C{1H} NMR spectroscopic studies show both similarities (n = 6) and differences (n = 4, 2) to previously characterised examples of fulleride complexes and materials with electropositive metal ions. The molecular structures of [{(Arnacnac)Mg}nC60] with n = 6, 4 and 2 can be described as inverse coordination complexes of n [(Arnacnac)Mg]+ ions with C60n anions showing predominantly ionic metal–ligand interactions, and include the first well-defined and soluble complexes of the C606− ion. Experimental studies show the flexible ionic nature of the {(Arnacnac)Mg}+⋯C606− coordination bonds. DFT calculations on the model complex [{(Menacnac)Mg}6C60] (Menacnac = HC(MeCNMe)2) support the formulation as an ionic complex with a central C606− anion and comparable frontier orbitals to C606− with a small HOMO–LUMO gap. The reduction of C60 to its hexaanion gives an indication about the reducing strength of dimagnesium(I) complexes.

Graphical abstract: Hydrocarbon-soluble, hexaanionic fulleride complexes of magnesium

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Publication details

The article was received on 02 Aug 2019, accepted on 06 Oct 2019 and first published on 09 Oct 2019


Article type: Edge Article
DOI: 10.1039/C9SC03857D
Chem. Sci., 2019, Advance Article
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    Hydrocarbon-soluble, hexaanionic fulleride complexes of magnesium

    S. R. Lawrence, C. A. Ohlin, D. B. Cordes, A. M. Z. Slawin and A. Stasch, Chem. Sci., 2019, Advance Article , DOI: 10.1039/C9SC03857D

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