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首页> 外文期刊>Helvetica chimica acta >Dynamic phenomena in self-complementary {2}-metallocryptates probed by solution ~(133)Cs-NMR. New insights into ion pairing processes: X-ray structure and solid-state NMR spectra of a meandering species
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Dynamic phenomena in self-complementary {2}-metallocryptates probed by solution ~(133)Cs-NMR. New insights into ion pairing processes: X-ray structure and solid-state NMR spectra of a meandering species

机译：溶液〜（133）Cs-NMR探测自互补{2}-金属矿的动态现象。离子配对过程的新见解：弯曲物种的X射线结构和固态NMR光谱

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摘要

Two self-complementary {2}-metallocryptates, differing in methyl and phenyl substituents, respectively, have been studied by X-ray analysis, and solid-state and solution NMR. Mixed Mg/Cs metal methyl complex 2 is a linear polymer in the solid state. The two different Cs sites are confirmed by ~(133)Cs-solid-state NMR. By contrast, the analog mixed Mg/Cs metal phenyl complex 4 is a meandering polymer as shown by an actual X-ray analysis. The four non-equivalent Cs-sites in 4 are reflected in the solid-state NMR spectra. Solution ~(133)Cs-NMR spectra of 4 reveal two independent dynamic processes: a fast exchange of Cs within contact ion-pairs and solvent-separated ion-pairs (CIP, SSIP), and a slower exchange of 'inside' endo Cs, surrounded by three ligands, and 'outside' exo Cs involved in the CIP/SSIP equilibrium. Complete line-shape analysis of variable-temperature ~(133)Cs-NMR spectra of 4 yield kinetic parameters of =10.8kcal/mol for the fast SSIP-CIP exchange and =13.2kcal/mol for the slower endo/exo exchange of Cs. DOSY-NMR Measurements confirm the monomeric nature of 4 in solution.
机译：通过X射线分析以及固态和溶液NMR研究了分别在甲基和苯基取代基方面不同的两种自互补{2}-金属锂。混合的Mg / Cs金属甲基络合物2是固态的线性聚合物。通过〜（133）Cs-固态NMR确认了两个不同的Cs位点。相反，如实际的X射线分析所示，模拟的混合的Mg / Cs金属苯基络合物4是曲折的聚合物。固态NMR光谱反映了4个中的四个非等价Cs位。 4的溶液〜（133）Cs-NMR光谱揭示了两个独立的动力学过程：接触离子对和溶剂分离离子对（CIP，SSIP）中Cs的快速交换，以及内部“内” Cs的较慢交换，被三个配体包围，并且参与CIP / SSIP平衡的“外部” exoC。完整的线形分析可变温度〜（133）Cs-NMR谱图，对于快速SSIP-CIP交换，四个产率动力学参数为= 10.8kcal / mol，对于较慢的Cs内/外交换，为= 13.2kcal / mol 。 DOSY-NMR测量证实了溶液中4的单体性质。

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