Dankert Fabian, Richter Roman-Malte, Weigend Florian, Xie Xiulan, Balmer Markus, von Hänisch Carsten
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse 4, 35032, Marburg, Germany.
Angew Chem Int Ed Engl. 2021 Apr 26;60(18):10393-10401. doi: 10.1002/anie.202014822. Epub 2021 Mar 23.
We herein report the synthesis, structures, coordination ability, and mechanism of formation of silicon analogs of crown ethers. An oligomerization of D (I) ( D ,=(Me Si O) ) was achieved by the reaction with GaI and MI (M=Li, Na, Mg, Ca, Sr). In these reactions the metal cations serve as template and the anions (I /[GaI ] ) are required as nucleophiles. In case of MI =LiI, [Li( D )GaI ] (1) is formed. In case of MI =NaI, MgI , CaI , and SrI the compounds [M( D )(GaI ) ] (M=Mg (3), Ca (4), Sr (5) are obtained. Furthermore the proton complex [H( D )][Ga I ] (6) was isolated and structurally characterized. All complexes were characterized by means of multinuclear NMR spectroscopy, DOSY experiments and, except for compound 3, also by single crystal X-ray diffraction. Quantum chemical calculations were carried out to compare the affinity of M to D and other ligands and to shed light on the formation of larger rings from smaller ones.
我们在此报告冠醚硅类似物的合成、结构、配位能力及形成机理。通过与GaI和MI（M = Li、Na、Mg、Ca、Sr）反应实现了D（I）（D =(MeSi O) ）的低聚反应。在这些反应中，金属阳离子作为模板，阴离子（I /[GaI ] ）作为亲核试剂。当MI = LiI时，形成[Li( D )GaI ]（1）。当MI = NaI、MgI 、CaI 和SrI时，得到化合物[M( D )(GaI ) ]（M = Mg（3）、Ca（4）、Sr（5））。此外，质子络合物[H( D )][Ga I ]（6）被分离并进行了结构表征。所有络合物均通过多核NMR光谱、DOSY实验进行表征，除化合物3外，还通过单晶X射线衍射进行表征。进行了量子化学计算，以比较M对D和其他配体的亲和力，并阐明由较小环形成较大环的过程。
