多金属化碱金属杯芳烃[M4(p-叔丁基杯[4]芳烃-4H)(thf)x]2.n THF（M = Li，K；n = 6或1；x = 4或5）和[Li2(p-叔丁基杯[4]芳烃-2H)(H2O)(μ-H2O)(thf)].3 THF的合成与结构分析

Synthesis and structural analysis of the polymetallated alkali calixarenes [M4(p-tert-butylcalix[4]arene-4H)(thf)x]2.n THF (M=Li, K; n=6 or 1; x=4 or 5) and [Li2(p-tert-butylcalix[4]arene-2H)(H2O)(mu-H2O)(thf)].3 THF.

作者信息

Gueneau Estelle D, Fromm Katharina M, Goesmann H

机构信息

University of Geneva, Sciences II 30, Quai Ernest-Ansermet, 1211 Geneva 4, Switzerland.

出版信息

Chemistry. 2003 Jan 20;9(2):509-14. doi: 10.1002/chem.200390053.

DOI:10.1002/chem.200390053

PMID:12532300

Abstract

To study the structures and reactivities of alkali metallated intermediates of calix[4]arenes, three compounds were isolated: Li(4)(p-tert-butylcalix[4]arene-4H)(thf)(4).6 THF (1), [Li(2)(p-tert-butylcalix[4]arene-2H)(H(2)O)(mu-H(2)O)(thf)].3 THF (2), and K(4)(p-tert-butylcalix[4]arene-4H)(thf)(5).THF (3). The structure of 1 is shown to be dependent on the coordinating solvent. Partial hydrolysis of 1 leads to the formation of 2. The potassium compound 3 features a different structure to that of 1, due to a higher coordination number as well as stronger cation-pi-bonding interactions.

摘要

为研究杯[4]芳烃碱金属化中间体的结构和反应活性，分离出了三种化合物：Li(4)(对叔丁基杯[4]芳烃-4H)(thf)(4).6 THF (1)、[Li(2)(对叔丁基杯[4]芳烃-2H)(H₂O)(μ-H₂O)(thf)].3 THF (2) 和 K(4)(对叔丁基杯[4]芳烃-4H)(thf)(5).THF (3)。结果表明，1的结构取决于配位溶剂。1的部分水解导致2的形成。钾化合物3具有与1不同的结构，这是由于其配位数更高以及阳离子-π键相互作用更强。