Cobalt bis(dicarbollides)(1-) covalently attached to the calix[4]arene platform:: The first combination of organic bowl-shaped matrices and inorganic metallaborane cluster anions
Cobalt bis(dicarbollides)(1-) covalently attached to the calix[4]arene platform:: The first combination of organic bowl-shaped matrices and inorganic metallaborane cluster anions
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DOI：
10.1002/ejoc.200400811
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发表时间：
2005-05-13
影响因子：
2.8
通讯作者：
Ungaro, R
中科院分区：
文献类型：
--
作者：
Grüner, B;Mikulásek, L;Ungaro, R
首次合成了不同的杯[4]芳烃和间苯二酚[4]芳烃双（二羧酸）钴阴离子取代的离子化合物（1）。从tBu-杯[4]芳烃（A）出发，通过与1-二氧六环衍生物[8-O（CH_2-CH_2）（2）O（+）-1，2-C_2B_9 H_（10）]的O-烷基化反应，得到了一系列在其下缘（36）上带有1 ~ 4个簇阴离子的单、二、三、四取代衍生物的碱金属盐（1 '，2'-C2B 9 H11）-3，3 '-Co]（2），均为顺式或锥式异构体。与此相反，tBu-杯[4]芳烃的二丙醚（B）的双取代分别导致锥形和1，3-交替构象异构体7a和7 B的混合物。从在上边缘通过远端位置的羧酸基团官能化的四丙氧基-杯[4]芳烃（C）和氨基桥连衍生物[8，8 ′-μ-H2 N
Various calix[4]arene and resorc[4]arene ionic compounds substituted by cobalt bis(dicarbollide) anions (1) have been prepared for the first time. From tBu-calix[4]arene (A) the complete series of mono-, di-, tri- and tetrasubstituted derivatives bearing one to four cluster anions on the lower rim (36) have been obtained in the form of their alkali-metal salts by O-alkylation with the 1-dioxane derivative [8-O(CH2-CH2)(2)O(+)-1,2-C2B9H10)-(1',2'-C2B9H11)-3,3'-Co] (2), all of which are syn or cone isomers. In contrast, disubstitution of the dipropyl ether of tBu-calix[4]arene (B) led to a mixture of the cone and 1,3-alternate conformers 7a and 7b, respectively. Starting from tetrapropoxy-calix[4]arene functionalised at the upper rim by carboxylic acid groups in distal positions (C) and an amino-bridged derivative [8,8'-mu-H2N