杂化二硅冠醚的稳定碱金属配合物
Stable Alkali-Metal Complexes of Hybrid Disila-Crown Ethers.
作者信息
Reuter Kirsten, Buchner Magnus R, Thiele Günther, von Hänisch Carsten
机构信息
Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Philipps-Universität Marburg , Hans-Meerwein-Straße 4, 35032 Marburg, Germany.
Department of Chemistry, University of California , 210 Lewis Hall, Berkeley, California 94720, United States.
出版信息
Inorg Chem. 2016 May 2;55(9):4441-7. doi: 10.1021/acs.inorgchem.6b00267. Epub 2016 Apr 15.
The complexation ability of hybrid disilane and ethylene containing crown ether ring systems was analyzed using 1,2-disila[12]crown-4 (1), 1,2-disila[15]crown-5 (2), 1,2-disila[18]crown-6 (3), and 1,2,7,8-tetrasila[12]crown-4 (7). Alkali-metal complexes (Li(+), Na(+), K(+)) were obtained and analyzed via X-ray diffraction. The complex stability of Li(1,2-disila[12]crown-4) and Li(1,2,7,8-tetrasila[12]crown-4) was determined, in relation to the lithium complex of [12]crown-4, by density functional theory (DFT) calculations employing the BP86/def2-TZVP level of theory. In solution, the exchange of lithium cations between pure [12]crown-4 and hybrid [12]crown-4 is on even terms, as has been shown from the relative binding affinity of compounds 1 and 7 by means of dynamic proton nuclear magnetic resonance (NMR) spectroscopy.
使用1,2-二硅[12]冠-4（1）、1,2-二硅[15]冠-5（2）、1,2-二硅[18]冠-6（3）和1,2,7,8-四硅[12]冠-4（7）分析了含冠醚环系统的杂化乙硅烷和乙烯的络合能力。通过X射线衍射获得并分析了碱金属配合物（Li(+)、Na(+)、K(+)）。采用BP86/def2-TZVP理论水平的密度泛函理论（DFT）计算，相对于[12]冠-4的锂配合物，确定了Li(1,2-二硅[12]冠-4)和Li(1,2,7,8-四硅[12]冠-4)的配合物稳定性。在溶液中，纯[12]冠-4和杂化[12]冠-4之间锂阳离子的交换是均等的，这已通过动态质子核磁共振（NMR）光谱法对化合物1和7的相对结合亲和力得以证明。
Zotero 插件