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Studies on the synthesis for selective reagents for metal separation and their application to analytical chemistry.

金属分离选择性试剂的合成及其在分析化学中的应用研究。

基本信息

批准号：
63470030
负责人：
MATSUI Masakazu
金额：
$ 3.46万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1988
资助国家：
日本
起止时间：
1988 至 1989
项目状态：
已结题

项目摘要

There is, at present, a need for a rational approach toward ligand design for selective complexation of metals in solution not only in the field of analytical chemistry but in other several branches of science, such as therapeutic reagents for metal intoxication, design of antibiotics, assign of imaging agents in the body, metal extractants in hydrometallurgy, metal sequesting agents in detergents, biological cation transport systems and environmental chemistry. It is necessary to find out a rigid new ligand for coordinating space and/or to prepare the ligand having a novel function by introducing, e.g., sterically hindered group to it in order to get more selective chelating agents.The present report describes chiefly thermal properties and extractions of metal polypyrazolylborate chelates and extractions of such organometallic compounds as organogermanium species. Four polypyrazolylborate ligands, HB(Me_2PY)_3^-, HBpz_3^-, Bpz_4^- and H_2Bpz_2^-, were synthesized, and these chelates of the first transition metals and IIA group metals were characterized by thermal analysis and complementary techniques. Relative thermal stability decreases in the order of the shielding degree of the ligands, HB(Me_2pz)_3^- > HBpz_3^- > Bpz_4^- > H_2Bpz_2^-. The most striking aspect of the present results was that Mg chelates of HB(ME_2PY)_3^- and HBpz_3^- were easily sublimed. The extractions of metals with such novel acylpyrazolones as bis(acylpyrazolone) derivatives and acylpyrazolones with bulky substituents, were also studied.The extractions of organogermanium such as mono- and tri-methyl germanium (MMGe, TMGe) and monophenyl germanium (MPGe) species from hydrogen and/or lithium chloride solution into chloroform or carbon tetrachloride phase were performed. The formation constants between the organogermanium species and halogenide ions were determined by the extraction method.

目前，不仅在分析化学领域，而且在其他几个科学分支中，如金属中毒的治疗试剂、抗生素的设计、体内显像剂的分配、湿法冶金中的金属萃取剂、洗涤剂中的金属螯合剂、生物阳离子运输系统和环境化学。有必要找到用于配位空间的刚性新配体和/或通过引入，例如，本文主要介绍了聚吡唑硼酸金属螯合物的热性能、萃取性能以及有机锗等有机金属化合物的萃取性能。合成了四个聚吡唑硼酸酯配体HB（Me_2PY）_3^-、HBpz_3^-、Bpz_4^-和H_2Bpz_2^-，并通过热分析和互补技术对这些第一过渡金属和IIA族金属的螯合物进行了表征。相对热稳定性随配体屏蔽程度的增加而降低，HB（Me_2pz）_3^- > HBpz_3^- > Bpz_4^- > H_2Bpz_2^-。最引人注目的是HB（ME_2PY）_3^-和HBpz_3^-的镁螯合物易于升华。研究了新型酰基吡唑啉酮衍生物（双酰基吡唑啉酮衍生物和大取代基酰基吡唑啉酮衍生物）对金属的萃取作用，考察了它们对有机锗（MMGe、TMGe和MPGe）的萃取性能。用萃取法测定了有机锗与卤离子的形成常数。