Issue 46, 2019

Hydrocarbon-soluble, hexaanionic fulleride complexes of magnesium


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

Supplementary files

Article information

Article type
Edge Article
02 Aug 2019
06 Oct 2019
First published
09 Oct 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2019,10, 10755-10764

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, 10, 10755 DOI: 10.1039/C9SC03857D

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity