Mechanistic insights of anionic ligand exchange and fullerene reduction with magnesium(i) compounds.
Mechanistic insights of anionic ligand exchange and fullerene reduction with magnesium(i) compounds.
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DOI：
10.1039/c9dt03976g
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发表时间：
2019-11
影响因子：
4
通讯作者：
S. R. Lawrence;D. Cordes;A. Slawin;A. Stasch
中科院分区：
文献类型：
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作者：
S. R. Lawrence;D. Cordes;A. Slawin;A. Stasch
配合物的组合之间的配体交换反应[{其中Ar = 2，6-iPr 2C 6 H3（Dip）、2，6-Et 2C 6 H3（Dep）、2，4，6-Me 4C 6 H2（Mes）和2，6-Me 2C 6 H3（Xyl），[在氘代芳香族和脂肪族溶剂以及四氢呋喃中研究了[{Ph 2 P（NDip）2}Mg）2]、[（Arnacnac）Li]（其中Ar = Mes或Xyl）和[{Ph 2 P（NDip）2}Li]。反应得到具有不对称取代的二镁（i）络合物的产物混合物。（Arnacnac）MgMg（Ar'nacnac）]，其中Ar、Ar' = Dip、Dep、Mes、Xyl和[{Ph 2 P（NDip）2}MgMg（Arnacnac）]，其中Ar = Mes或Xyl，并且表明阴离子配体在Mg 22+离子上的交换通过缔合机制进行，并且强烈依赖于配体空间和配体形状，并且可以非常迅速。富勒烯C60被二镁（i）络合物[{（Arnacnac）Mg}2]和[（{Ph 2 P（NDip）2}Mg）2]活化成富勒烯络合物的反应类似地取决于配体空间和配体形状，但可能不涉及富勒烯在其还原之前与二镁（i）化合物中的Mg中心的直接配位。合成了C606富勒烯配合物[（{Ph 2 P（NDip）2}Mg）6C 60]，并对其进行了光谱和结构表征。
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.