Institut für Chemie, Karl-Franzens-Universität Graz, Schubertstrasse 1, 8010 Graz, Austria.
Chemistry. 2009 Sep 21;15(37):9521-9. doi: 10.1002/chem.200900915.
The synthesis of a series of m-terphenyl-substituted tetrafluorosilicates with different cations (Na(+), K(+), Rb(+), Cs(+), Ag(+), Tl(+)) is described and the interactions between the anion and cation are investigated in the solid, solution, and gas states by using multinuclear NMR spectroscopy, X-ray diffraction, and ion cyclotron resonance Fourier-transform mass spectrometry (ICR-FT-MS). In solution, heteronuclear NMR spectroscopy parameters show only limited sensitivity to the nature of the cation, which furthermore can be affected by solvent effects. More pronounced effects are observed in the structural data obtained from X-ray diffraction studies, which are in good agreement with experimental gas-phase data from ESIMS. ESIMS also reveals the existence of dimeric species of the type M(DmpSiF(4))(2) (Dmp = 2,6-dimesitylphenyl), the stability of which was determined by normalized collision energy experiments.
描述了一系列具有不同阳离子（Na(+)、K(+)、Rb(+)、Cs(+)、Ag(+)、Tl(+)）的 m-三联苯取代的四氟硅酸盐的合成，并通过使用多核 NMR 光谱、X 射线衍射和离子回旋共振傅里叶变换质谱（ICR-FT-MS）研究了在固态、溶液和气态中阴离子和阳离子之间的相互作用。在溶液中，异核 NMR 光谱参数对阳离子的性质仅表现出有限的敏感性，而且溶剂效应也会影响这些参数。在 X 射线衍射研究中获得的结构数据中观察到更明显的影响，这些数据与从 ESIMS 获得的实验气相数据吻合良好。ESIMS 还揭示了[M(DmpSiF(4))(2)]-（Dmp = 2,6-二异丙基苯基）类型的二聚体的存在，其稳定性通过归一化碰撞能实验确定。
