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Studies on Polydentate Organic Phosphorus Compounds as Extraction Reagents.

多齿有机磷化合物作为萃取剂的研究。

基本信息

批准号：
01540475
负责人：
UMETANI Shigeo
金额：
$ 1.02万
依托单位：
Kyoto Uneversity
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1989
资助国家：
日本
起止时间：
1989 至 1990
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-01540475/
关键词：
Solvent Extraction Ion pair Extraction Chelate Extraction Synergic Effect Phosphine Oxide Polydentate Ligand Alkaline Earth Metal Divalent Transition Metal 遷移金属分離化学金属イオンイオン対有機リン化合物中性配位子キレ-ト試薬

项目摘要

The following polydentate phosphine oxides have been synthesized in the present work and their possible use as extraction reagents has been examined being compared with the monodentate ligand, Trioctylphosphine oxide (TOPO). Tetraphenyldiphosphine dioxide (TPDPDO), bis (diphenylphosphinyl) methane (BDPPM) and ethane (BDPPE) as bidentate ligands, and tris (diphenylphosphinyl) methane (TDPPM) as a tridentate ligand.The ion pair extraction of divalent metals with these phosphine oxides and a bulky anion has been investigated. It was found that alkaline earths (Mg, Ca, Sr and Ba) and some divalent transition metals (Co, Ni, Cu, Zn and Cd) are readily extracted with BDPPM or TDPPM and perchlorate or picrate ion. The extraction with TOPO or BDPPE was very poor. Six-membered ring which is known to be very stable is formed when BDPPM or TDPPM attaches to a metal ion, whereas seven-membered ring is expected with BDPPE. Precipitate was observed at the benzene/water interface in the BDPPM/ClO_4 system. Picrate is a suitable anion rather than perchlorate. The compositions of the extracted species were obtained by a graphical method.The synergic extraction of divalent metals with 1-Phenyl-3-Methyl-4-Benzoyl-5-Pyrazolone (HPMBP) or 4-trifluoroacetyl-5-pyrazolone (HPMTFP) and phosphine oxides has also been examined. BDPPM was found to be a much more powerful adduct forming ligand than TOPO and BDPPE. TDPPM is considered to work as a bidentate ligand in the synergic extraction of alkaline earths. The stability of the adduct forming reaction and the number of neutral ligand participating in the reaction could be interpreted in terms of the vacant coordination number, the size of room allowed for the neutral ligand and the molecular structure of the neutral ligand.

本工作合成了以下多齿氧膦化合物，并与单齿配体三辛基氧膦(TOPO)进行了比较，考察了它们作为萃取剂的可能性。以四苯基二膦(TPDO)、二(二苯基膦)甲烷(BDPPM)和乙烷(BDPPE)为双齿配体，三(二苯基膦)甲烷(TDPPM)为三齿配体。结果表明，BDPPM或TDPPM与高氯酸盐或苦味酸根离子均能很好地萃取碱土(镁、钙、锶、钡)和一些二价过渡金属(钴、镍、铜、锌、镉)。TOPO或BDPPE的萃取率很低。当BDPPM或TDPPM结合到金属离子上时，会形成已知非常稳定的六元环，而BDPPE则期望形成七元环。在BDPPM/ClO_4体系中，苯/水界面有沉淀生成。苦味酸盐是一种合适的阴离子，而不是高氯酸盐。研究了1-苯基-3-甲基-4-苯甲酰基-5-吡唑啉酮(HPMBP)或4-三氟乙酰基-5-吡唑啉酮(HPMTFP)对二价金属的协同萃取作用。BDPPM是一种比TOPO和BDPPE更强的加合物形成配体。TDPPM被认为是碱土协同萃取剂中的双齿配体。加合物形成反应的稳定性和参与反应的中性配体数目可以用中性配体的空位配位数、允许的空间大小和中性配体的分子结构来解释。