水溶液中N-三(2-氨基乙基)胺-N',N',N'', N'',N''',N'''-六乙酸与U(Ⅵ)的配位化学研究

Coordination Chemistry of U(Ⅵ) and N-tris(2-aminoethyl)amino-N',N',N'',N'',N''',N'''-hexaacetic Acid in Aqueous Solution

  • 摘要: 铀是天然大量存在的两种锕系元素之一,在水溶液和有氧条件下,通常以正六价的铀酰离子形式存在。N-三(2-氨基乙基)胺-N',N',N'',N'',N''',N'''-六乙酸(TTAHA,H6L)是一种氨基多羧酸类配体,可以多种模式与不同金属离子配位,目前尚未见有关TTAHA与铀配位化学研究的报道。本工作在温度为25 ℃、离子强度为1.0 mol/L NaClO4条件下,通过电位滴定法,测得TTAHA的7级质子化常数。同时,结合电位滴定法和紫外可见吸收光谱法,确定TTAHA-U(Ⅵ)体系存在5种配合物,分别为(UO2)2LH2、(UO2)2LH、UO2LH3−、UO2L4−和UO2L(OH)5−。在此基础上测定了各配合物的稳定常数,并获得其摩尔吸收光谱。通过拉曼光谱法,结合相关文献资料分析,推测了TTAHA-U(Ⅵ)配合物结构:(UO2)2LH呈O-N-O三配位模式、UO2LH3−呈O-N-N-O四配位模式。所得数据为TTAHA与铀酰离子的配位作用研究提供了基础参数,其配合物组成、稳定常数及配位模式的确定,为理解氨基多羧酸类配体与铀的相互作用机制提供了理论依据。

     

    Abstract: Uranium, as one of the actinide metal elements with relatively high abundance in nature, its natural existence forms are of great significance for research on environmental and chemical behaviors. Typically, it exists in the +6 oxidation state as \mathrmUO_2^2+ , especially in aqueous solutions under aerobic conditions. N-tris(2-aminoethyl)amine-N',N',N'',N'',N''',N'''-hexaacetic acid (TTAHA, H6L), as a typical amino polycarboxylic acid ligand, exhibits rich coordination ability and diversity due to its multiple coordinating groups. It can form stable coordination complexes with different metal ions through various binding modes, depending on their charge, radius, and other characteristics. However, based on a review of current literature, although the TTAHA ligand has been widely studied with various metal ions, detailed chemical research on its coordination mechanism with uranium has not been systematically reported, and this field remains in the exploratory stage. In this paper, potentiometry was used to determine the seven protonation constants of TTAHA at I_\mathrmN\mathrma\mathrmC\mathrml\mathrmO_4 =1.0 mol/L. Subsequently, a combination of potentiometry and spectrophotometry identified five U(Ⅵ)-TTAHA complexes, namely (UO2)2LH2, (UO2)2LH, UO2LH3−, UO2L4−, and UO2L(OH)5−. The stability constants and molar absorption spectra of these complexes were calculated. The structures of the U(Ⅵ)-TTAHA complexes were inferred using Raman spectroscopy. The (UO2)2LH complex adopts O-N-O tridentate coordination, involving two oxygen atoms from two carboxylic groups and one nitrogen atom from the amine group. Furthermore, the UO2LH3− complex exhibits O-N-N-O tetradentate coordination. In summary, the systematic data obtained in this study, including protonation constants, the precise chemical composition of each uranyl complex and their corresponding stability constants, as well as the molar absorption spectra of key representative complex species. The obtained data provide basic parameters for the study of the coordination interaction between TTAHA and uranium ions. The determination of the complex composition, stability constants, and coordination patterns provides experimental and theoretical basis for understanding the interaction mechanism between amino polycarboxylic acid ligands and uranium.

     

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