Arras Janet, Kruczyński Tomasz, Bresien Jonas, Schulz Axel, Schnöckel Hansgeorg
Institut für Anorganische Chemie, Karlsruher Institut für Technologie (KIT), Engesserstrasse 15, 76131, Karlsruhe, Germany.
Institut für Chemie, Universität Rostock, Albert-Einstein-Strasse 3a, 18059, Rostock, Germany.
Angew Chem Int Ed Engl. 2019 Jan 14;58(3):716-721. doi: 10.1002/anie.201811053. Epub 2018 Nov 27.
Magnesium(I) halides (Mg X; X=Cl, Br, I), as high temperature molecules, are trapped and finally stored at -80 °C in toluene/donor solutions. These solutions provide insights into the fundamental mechanism of reduction reactions using activated magnesium metal as a prototype for every base metal. The most important example of such a reaction is the preparation of Grignard reagents (RMgX). The details of this highly complex mechanism especially of intermediates between Mg metal and Mg (RMgX) remain unknown until today. The same is true for the reaction of bulk magnesium with Group 15 halide compounds that give biradicaloid species. We investigate the reduction of P-Cl bonds with solutions of [Mg Br(N Bu )] (1). The phosphanes [ClP(μ-NTer)] (2) and (Me Si) N-PCl (3), were chosen as they had successfully been reduced by Mg metal before. Furthermore, reactions of both 1 and Mg metal are compared with an Mg chelate complex L Mg-MgL containing a strong Mg-Mg σ-bond.
卤化镁（I）（MgX；X = Cl、Br、I）作为高温分子，被捕获并最终在-80°C下储存于甲苯/给体溶液中。这些溶液为以活性镁金属作为每种贱金属原型的还原反应基本机制提供了见解。此类反应最重要的例子是格氏试剂（RMgX）的制备。直到如今，这种高度复杂机制的细节，尤其是镁金属与Mg（RMgX）之间中间体的细节仍不清楚。大量镁与生成双自由基类物种的第15族卤化物化合物的反应情况也是如此。我们用[Mg Br（N Bu）]（1）溶液研究P-Cl键的还原反应。选择膦[ClP（μ-NTer）]（2）和（Me Si）N-PCl（3），因为它们之前已被镁金属成功还原。此外，将1和镁金属的反应与含有强Mg-Mg σ键的镁螯合物L Mg-MgL的反应进行比较。
