锂和钠大环(乙基对叔丁基杯(4)芳烃四乙酸酯,隐式和222冠醚)体系的溶液和配位焓(固态)

A. F. Namor, L. E. P. Salazar, M. A. L. Tanco, D. Kowalska, Jose A. Villanueva Salas, R. A. Schulz
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引用次数: 8

摘要

在298.15 K的乙腈中分离了一系列对叔丁基杯(4)芳烃四乙酸锂和钠盐,并对其进行了热化学表征。还报告了普通钠盐(四氟硼酸盐、三氟甲磺酸盐、碘化物和溴化物)在同一温度下在该溶剂中的标准溶液焓。将游离盐和络合盐以及配体的溶液数据与适当阳离子和乙腈大环的络合数据相结合,得出产物和反应物处于固态的过程中这些体系的配位焓。将锂、杯(4)芳烃酯和密码体222与冠醚的数据进行比较,反映出与冠醚相比,前者配体的正负离子相互作用明显减弱。结果表明,对于给定的配体和金属阳离子,阴离子效应反映在配位焓上。另一方面,对于含有相同配体和阴离子的体系,从锂到钠的焓稳定性降低。强调需要获得这些配体及其金属离子络合盐的晶格焓的实验数据。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Solution and co-ordination enthalpies (solid state) of lithium and sodium macrocycle (ethyl p-tert-butylcalix(4)arene tetraethanoate, cryptand 222 and crown ethers) systems
A series of lithium and sodium ethyl p-tert-butylcalix(4)arene tetraethanoate and cryptand 222 salts has been isolated and thermochemically characterised in acetonitrile at 298.15 K. Also reported are the standard enthalpies of solution of common sodium salts (tetrafluoroborate, trifluoromethanesulfonate, iodide and bromide) in this solvent at the same temperature. Solution data for the free and the complexed salts and for the ligand are combined with complexation data for the appropriate cation and macrocycle in acetonitrile to derive the enthalpies of co-ordination of these systems for the process where the product and the reactants are in the solid state. Comparison of data involving lithium and the calix(4)arene ester and the cryptand 222 with those for crown ethers reflects considerable weakening of cation–anion interactions in the former ligands relative to crown ethers. It is concluded that for a given ligand and metal cation, the anion effect is reflected in the co-ordination enthalpies. On the other hand, for systems containing the same ligand and anion, there is a decrease in enthalpic stability in moving from lithium to sodium. The need to obtain experimental data on crystal lattice enthalpies of these ligands and their metal ion complex salts is emphasised.
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