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首页> 外文期刊>Chemistry: A European journal >Alkali and Alkaline-Earth-M,etalated Forms of Calix[4]arenes: Synthons in the Synthesis of Transition Metal Complexes
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Alkali and Alkaline-Earth-M,etalated Forms of Calix[4]arenes: Synthons in the Synthesis of Transition Metal Complexes

机译：杯[4]芳烃的碱和碱土-M的平衡形式：过渡金属配合物合成中的合成子

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摘要

This is first coherent report on the metalation of calix[4]arene by alkali and alkaline-earth metals, thus providing a high-yield production of appropratie synthons for the synthesis of transition metal calix[4]arenes. In addition, various facets of the coordination chemistry by calix[4]arene anions oof alkali and alkaline-earth metal ions have been singled out. among them:1) the exo and endo coordination of metal ions by the calix[4]arene skeleton; 2) the #pi# solvation of the ions by the phenyl rings; 3) the ion-carrier properties of metal-lacalix[4]arenes; 4) the simulation of the kinetically labile coordination sphere of alkali and alkaline-earch metal ions by a polyoxo rigid skeleton. The peculiarties of the complexation of alkali and alkaline-earch metal ions yb calix[4]arenes outlined are deduced from the synthesis and the structural characterization both in solution (~1H NMR) and in the solid state (X-ray structure analysis) of the following classes of compounds; 1) [ptBu-calix[4](OMS_n)_4]_2 (M=Li, Na, K); 2) (p-tBu-calix[4])(OR)_2(O)_2ML] (M=Mg, L=THF, R=C_5H_9; M=Ca, L=TMEDA (tetramethylethylenediamine), R=C_5H_9; M=Ca, L=DME (dimethoxyethane), R=C_5H_9; M=Ba, L=TMEDA, R=C_5H_9; M=Ba, L=none, R=C_5H_9); 3) [p-tBu-calix[4](OC_5H_9)_2(O)-2Ca_2I_2(MeCN)_2]; 4) [{p-tBu-calix[4](OR)_2(O)_2}_2BaNa_2].
机译：这是有关碱金属和碱土金属对杯[4]芳烃金属化的首次连贯报道，从而为合成过渡金属杯[4]芳烃提供了合适产率的合成子。此外，通过碱和碱土金属离子的杯[4]芳烃阴离子已经筛选出配位化学的各个方面。其中：1）杯[4]芳烃骨架对金属离子的外向和内向配位; 2）离子被苯环＃pi＃溶剂化; 3）金属-lacalix [4]芳烃的离子载流子性质; 4）用多氧羰基刚性骨架模拟碱金属和碱金属离子的动力学不稳定配位球。概述了碱金属和碱金属金属离子yb calix [4]芳烃的络合特性，从溶液的〜（1H NMR）和固态（X射线结构分析）的合成和结构表征得出。以下几类化合物; 1）[ptBu-calix [4]（OMS_n）_4] _2（M = Li，Na，K）; 2）（p-tBu-calix [4]）（OR）_2（O）_2ML]（M = Mg，L = THF，R = C_5H_9; M = Ca，L = TMEDA（四甲基乙二胺），R = C_5H_9; M ＝ Ca，L ＝ DME（二甲氧基乙烷），R ＝ C_5H_9; M ＝ Ba，L ＝ TMEDA，R ＝ C_5H_9; M ＝ Ba，L ＝无，R ＝ C_5H_9）; 3）[p-tBu-calix [4]（OC_5H_9）_2（O）-2Ca_2I_2（MeCN）_2]; 4）[{p-tBu-calix [4]（OR）_2（O）_2} _2BaNa_2]。

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