NMR study of chemical species extracted and ligand-exchange reaction in the lanthanide(III)(NO3)3CMPO system
NMR study of chemical species extracted and ligand-exchange reaction in the lanthanide(III)(NO3)3CMPO system
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镧系元素(III)(NO3)3CMPO体系中化学物质提取和配体交换反应的NMR研究
DOI：
10.1016/0925-8388(94)90268-2
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发表时间：
1994
影响因子：
6.2
通讯作者：
C. Miyake
中科院分区：
文献类型：
--
作者：
Takashi Nakamura;C. Miyake
将辛基（苯基）-N，N-二异丁基氨甲酰基甲基氧化膦（CMPO）用于TRUEX过程，用31 P和13 C NMR研究了Ln（III）-CMPO配合物的配位行为以及Eu（III）和Gd（III）-CMPO体系的配体交换反应。结果表明，CMPO分子位于LnIII离子磁轴的赤道区，与LnIII··· O·P和LnIII··· O·C以双齿配位.虽然Ln（III）的cMPO配合物的几种异构体共存于CDCl 3，在室温下发生快速的分子内相互转化。在CDCl_3溶液中，与Eu Ⅲ和Gd Ⅲ离子配位的CMPO分子数分别为3个和2个。计算了配体交换反应的动力学参数ΔH* 和ΔS*。这些配体交换反应似乎通过解离（D）机制进行。
Octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) is used in the TRUEX process.31P and13C NMR measurements were carried out to study the behavior of coordination of Ln(III)CMPO complexes and the ligand exchange reaction for Eu(III) and Gd(III)CMPO systems. It was found that CMPO molecules locate in the equatorial region with respect to the magnetic axis of the LnIIIions and they coordinate to the central LnIIIions in a bidentate manner with LnIII··· O P and LnIII··· O C. Although several isomers for Ln(III)CMPO complexes co-exist in CDCl3, a rapid intramolecular interconversion occurs at room temperature. The numbers of CMPO molecules coordinated to EuIIIand GdIIIion were estimated to be 3 and 2, respectively, in CDCl3solution. The kinetic parameters,ΔH*andΔS*for the ligand exchange reactions were evaluated. These ligand exchange reactions seem to proceed through a dissociative (D) mechanism.