Alkali-Metalated Forms of Thiacalix[4]arenes

The alkali metal salts [TCALi4] (1), [TCANa4] (2), and [TCALK4] (3) of fully deprotonated p-tert-butyltetrathiacalix[4]arene (H4TCA) are readily available from the reactions of thiacalix[4]arene and n-BuLi, NaH, or KH as deprotonating
reagents. Crystals of the sodium salts 2 and the potassium salt 3 suitable for X-ray diffraction were obtained in the
form of the pyridine solvates [(TCA)2Na8·8py] (2·8py) and [(TCA)2K8·8py] (3·8py). These molecules are dimers in
the solid state but are structurally not related. In addition, the reaction of H4TCA and lithium hydroxide afforded the
structurally characterized complex [(TCA)Li5(OH)·4THF] (4). The molecular structure of 4 as well as the structures
of 2·8py and 3·8py reveal a close relationship to the corresponding alkali metal salts of the calix[4]arenes.

对完全去质子化的对叔丁基四硫代杯[4]芳烃（H₄TCA）的碱金属盐[TCALi₄]（1）、[TCANa₄]（2）与[TCALK₄]（3），可通过四硫代杯[4]芳烃分别以正丁基锂（n-BuLi）、氢化钠（NaH）或氢化钾（KH）作为去质子试剂反应便捷制备。适用于X射线衍射（X-ray diffraction）测试的钠盐2和钾盐3的晶体，以吡啶溶剂化物[(TCA)₂Na₈·8py]（2·8py）和[(TCA)₂K₈·8py]（3·8py）的形式获得。上述分子在固态下均为二聚体，但结构上并无关联。此外，H₄TCA与氢氧化锂反应可得到经结构表征的配合物[(TCA)Li₅(OH)·4THF]（4），其中THF即四氢呋喃（THF）。配合物4以及2·8py与3·8py的分子结构，与相应杯[4]芳烃的碱金属盐具有密切的结构相关性。