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

目前，不仅在分析化学领域，而且在其他几个科学分支领域，如金属中毒治疗试剂、抗生素设计、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等，都需要一种合理的方法来设计溶液中金属选择性络合的配体。为了获得选择性更强的螯合剂，有必要寻找一种刚性的新配体来配合空间和/或通过引入空间阻碍基团来制备具有新功能的配体。本报告主要描述了热性质和金属聚吡唑酸盐螯合物的提取，以及有机金属化合物如有机锗的提取。合成了HB(Me_2PY)_3^-、HBpz_3^-、Bpz_4^-和H_2Bpz_2^-四种聚吡唑硼酸盐配体，并用热分析和互补技术对第一过渡金属和IIA族金属的螯合物进行了表征。配体HB(Me_2pz)_3^- > HBpz_3^- > Bpz_4^- > H_2Bpz_2^-的相对热稳定性依次降低。本研究结果最显著的方面是HB(ME_2PY)_3^-和HBpz_3^-的Mg螯合物很容易升华。研究了双酰基吡唑酮衍生物和具有大取代基的酰基吡唑酮等新型酰基吡唑酮对金属的萃取。从氢和/或氯化锂溶液中提取有机锗，如单甲基锗、三甲基锗（MMGe、TMGe）和单苯基锗（MPGe），并将其萃取到氯仿或四氯化碳相。用萃取法测定了有机锗与卤化物离子之间的形成常数。

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.