Recognition of Some Lanthanides, Actinides, and Transition- and Heavy-Metal Cations by N-Donor Ligands: Thermodynamic and Kinetic Aspects
Recognition of Some Lanthanides, Actinides, and Transition- and Heavy-Metal Cations by N-Donor Ligands: Thermodynamic and Kinetic Aspects
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DOI：
10.1021/ic9010899
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发表时间：
2010-02-15
影响因子：
4.6
通讯作者：
Arnaud-Neu, Francoise
中科院分区：
文献类型：
--
作者：
Hubscher-Bruder, Veronique;Haddaoui, Jaouad;Arnaud-Neu, Francoise
显着的锕系元素（III）的多芳族N-供体双-三嗪-吡啶（BTP），半-双-三嗪-吡啶（hem-BTP）和双-三嗪-联吡啶（BTBP）的选择性，使这些配体的最有前途的候选人在分配和嬗变过程中开发到目前为止，以更好地管理核废料。研究了n-Pr-BTP、C（5）-hemi-BTP和两种最广泛研究的BTBP（C（5）-BTBP和CyMe（4）-BTBP）与一些代表性的镧系元素（III）、铀酰、钍和过渡金属及其他重金属阳离子在甲醇中的相互作用。使用紫外吸收分光光度法显示了不同化学计量的络合物的形成，其稳定性取决于配体和阳离子。用停流分光光度法研究了La（3+）、Eu（3+）和Yb（3+）与这四种配体的络合反应，测定了速率常数，并推测了可能的络合机理。
The remarkable actinide(III) selectivity of the polyaromatic N-donors bis-triazine-pyridines (BTPs), hemi-bis-triazine-pyridines (hem-BTPs) and bis-triazine-bipyridines (BTBPs) make these ligands the most promising candidates in partitioning and transmutation processes developed so far to better manage nuclear waste. The interactions of n-Pr-BTP, C(5)-hemi-BTP, and the two most extensively investigated BTBPs (C(5)-BTBP and CyMe(4)-BTBP) have been studied with some representative lanthanide(III), uranyl, thorium, and transition- and other heavy-metal cations in methanol. The formation of complexes of different stoichiometries, the stability of which depended on both the ligands and the cations, was shown using UV absorption spectrophotometry. Study of the complexation reactions of La(3+), Eu(3+) and Yb(3+) with these four ligands by stopped-flow spectrophotometry allowed determination of the rate constants and postulation of possible complexation mechanisms.