Mechanistic insights of anionic ligand exchange and fullerene reduction with magnesium(I) compounds
Abstract
Ligand exchange reactions between combinations of the complexes [{(Arnacnac)Mg}2], where Ar = 2,6-iPr2C6H3 (Dip), 2,6-Et2C6H3 (Dep), 2,4,6-Me4C6H2 (Mes), and 2,6-Me2C6H3 (Xyl), [({Ph2P(NDip)2}Mg)2], [(Arnacnac)Li], where Ar = Mes or Xyl, and [{Ph2P(NDip)2}Li] were studied in deuterated aromatic and aliphatic solvents, and tetrahydrofuran. The reactions afforded product mixtures with asymmetrically substituted dimagnesium(I) complexes [(Arnacnac)MgMg(Ar'nacnac)], where Ar, Ar' = Dip, Dep, Mes, Xyl and [{Ph2P(NDip)2}MgMg(Arnacnac)], where Ar = Mes or Xyl, and suggest that the exchange of anionic ligands on the Mg22+ ion proceeds via an associative mechanism and is strongly dependent on ligand sterics and ligand shape, and can be very rapid. The activation reaction of fullerene C60 by dimagnesium(I) complexes [{(Arnacnac)Mg}2] and [({Ph2P(NDip)2}Mg)2] to fulleride complexes is similarly dependent on ligand sterics and ligand shape, but likely does not involve direct coordination of the fullerene to the Mg centre in dimagnesium(I) compounds prior to its reduction. The new C606- fulleride complex [({Ph2P(NDip)2}Mg)6C60] was prepared, and spectroscopically and structurally characterised.
Citation
Lawrence , S , Cordes , D B , Slawin , A M Z & Stasch , A 2019 , ' Mechanistic insights of anionic ligand exchange and fullerene reduction with magnesium(I) compounds ' , Dalton Transactions , vol. In press . https://doi.org/10.1039/C9DT03976G
Publication
Dalton Transactions
Status
Peer reviewed
ISSN
1477-9226Type
Journal article
Rights
Copyright © 2019 The Author(s). This work has been made available online in accordance with publisher policies or with permission. Permission for further reuse of this content should be sought from the publisher or the rights holder. This is the author created accepted manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1039/C9DT03976G
Description
This work was supported by the University of St Andrews and the EPSRC (PhD studentship for SRL; EP/N509759/1).Collections
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