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Hydrocarbon-soluble, hexaanionic fulleride complexes of magnesium
Umeå University, Faculty of Science and Technology, Department of Chemistry.ORCID iD: 0000-0002-3804-6421
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2019 (English)In: Chemical Science, ISSN 2041-6520, E-ISSN 2041-6539, Vol. 10, no 46, p. 10755-10764Article in journal (Refereed) Published
Abstract [en]

The reaction of the magnesium(i) complexes [{((Ar)nacnac)Mg}(2)], ((Ar)nacnac = HC(MeCNAr)(2), Ar = Dip (2,6-iPr(2)C(6)H(3)), Dep (2,6-Et2C6H3), Mes (2,4,6-Me3C6H2), Xyl (2,6-Me2C6H3)) with fullerene C-60 afforded a series of hydrocarbon-soluble fulleride complexes [{((Ar)nacnac)Mg}(n)C-60], predominantly with n = 6, 4 and 2. C-13{H-1} 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 [{((Ar)nacnac)Mg}(n)C-60] with n = 6, 4 and 2 can be described as inverse coordination complexes of n [((Ar)nacnac)Mg](+) ions with C-60(n-) anions showing predominantly ionic metal-ligand interactions, and include the first well-defined and soluble complexes of the C-60(6-) ion. Experimental studies show the flexible ionic nature of the {((Ar)nacnac)Mg}+MIDLINE HORIZONTAL ELLIPSISC606- coordination bonds. DFT calculations on the model complex [{((Me)nacnac)Mg}(6)C-60] ((Me)nacnac = HC(MeCNMe)(2)) support the formulation as an ionic complex with a central C-60(6-) anion and comparable frontier orbitals to C-60(6-) with a small HOMO-LUMO gap. The reduction of C-60 to its hexaanion gives an indication about the reducing strength of dimagnesium(i) complexes.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2019. Vol. 10, no 46, p. 10755-10764
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:umu:diva-166814DOI: 10.1039/c9sc03857dISI: 000499471800009OAI: oai:DiVA.org:umu-166814DiVA, id: diva2:1382518
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The Kempe Foundations, JCK-1719Available from: 2020-01-03 Created: 2020-01-03 Last updated: 2020-01-03Bibliographically approved

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Ohlin, C. André

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