Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen (EKUT), Auf der Morgenstelle 18, 72076, Germany.
Dalton Trans. 2018 Sep 18;47(36):12546-12552. doi: 10.1039/c8dt01542b.
A compilation of solvent-free homometallic methyl compounds of the type MMex (x = 1-6) is provided and categorised according to their method of characterisation (powder or single crystal X-ray diffraction, gas electron diffraction (GED), reactivity, unconfirmed). Recrystallisation of polymeric [MgMe2]n from excess GaMe3 led to the formation of highly pure [MgMe2]n suitable for single crystal X-ray crystallographic studies. Transient Mg(GaMe4)2 could be detected in excess GaMe3 by NMR spectroscopy, but its isolation as Mg(GaMe4)2 failed. On one occasion tetrameric [Mg(GaMe4)(OMe)]4 could be isolated as a minor co-product. The formation of single-crystalline [MgMe2]n from a saturated ethereal solution could be reproduced as reported earlier by Coates et al. Assessing the reactivity of potassium methoxide methanol adduct toward Mg(AlMe4)2, the protonolysis reaction with MeOH gave unprecedented [Mg(AlMe4){Al(OMe)2Me2}]2 featuring one 8-membered [MgOAlO]2 metalloxane ring and two 4-membered metallacycles.
提供了溶剂自由同核甲基化合物 MMex（x=1-6）的汇编，并根据其表征方法（粉末或单晶 X 射线衍射、气体电子衍射（GED）、反应性、未确认）进行了分类。从过量 GaMe3 中重结晶聚合的[MgMe2]n 导致形成非常纯净的[MgMe2]n，适用于单晶 X 射线晶体学研究。通过 NMR 光谱可以检测到过量 GaMe3 中瞬态 Mg(GaMe4)2，但未能将其分离出来。有一次，四聚体[Mg(GaMe4)(OMe)]4 可以作为次要副产物分离出来。从饱和的醚溶液中生成单晶[MgMe2]n，可以如 Coates 等人之前报道的那样再现。评估甲醇钠甲醇加合物对 Mg(AlMe4)2 的反应性，与 MeOH 的质子解反应得到了前所未有的[Mg(AlMe4){Al(OMe)2Me2}]2，其特征为一个 8 元[MgOAlO]2 金属氧烷环和两个 4 元金属环。
