TY - JOUR
T1 - Mechanistic insights of anionic ligand exchange and fullerene reduction with magnesium(I) compounds
AU - Lawrence, Sam
AU - Cordes, David Bradford
AU - Slawin, Alexandra Martha Zoya
AU - Stasch, Andreas
N1 - This work was supported by the University of St Andrews and the EPSRC (PhD studentship for SRL; EP/N509759/1).
PY - 2019/10/29
Y1 - 2019/10/29
N2 - 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.
AB - 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.
U2 - 10.1039/C9DT03976G
DO - 10.1039/C9DT03976G
M3 - Article
SN - 1477-9226
VL - In press
JO - Dalton Transactions
JF - Dalton Transactions
ER -