NMR studies of mixed-ligand lanthanide (III) complexes. Peculiarities of molecular structure, dynamics and paramagnetic properties for cerium subgroup chelates with crown ethers

被引：16

作者：

Babailov, SP ^{[1
]}

Mainichev, DA ^{[1
]}

机构：

[1] Russian Acad Sci, SB, Radiospect Lab, Inst Inorgan Chem, Novosibirsk 630090, Russia

来源：

JOURNAL OF INCLUSION PHENOMENA AND MACROCYCLIC CHEMISTRY | 2002年 / 43卷 / 3-4期

基金：

俄罗斯基础研究基金会;

关键词：

complexes; crown ethers; dynamic NMR; enthalpy of activation; lanthanides; molecular dynamics;

D O I：

10.1023/A:1021237718495

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The molecular structure, dynamics and paramagnetic properties of the complex cations [Ln(ptfa)(2) (18-crown-6)](+) in deuterated toluene were studied for Ln = La, Ce, Pr and Nd. The activation enthalpy values of 68 +/- 5, 55 +/- 15 and 60 +/- 13 kJ mol(-1) for the 18-crown-6 conformational inversion processes for the complex cations of Ce, Pr and Nd, respectively, were obtained. Quantitative investigation of the lanthanide-induced chemical shifts shows a monotonic change of a spatial structure and magnetic susceptibility in comparison with the Bleaney predicted dependence. The free energy of molecular inversion activation for 18-crown-6 molecules in the complex cation [Ln(fod)(2)(18-crown-6)](+) is 74 +/- 9 kJ mol(-1) at 363 K, which is a little more than the value of the free energy of activation 64 +/- 9 kJ mol(-1) at 363 K in the complex cation [Ln( ptfa)(2)(18-crown-6)](+).

引用

页码：187 / 193

页数：7

共 30 条

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