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.

在本工作中已经合成了以下多源磷酸氧化物，并将其作为提取试剂的使用与单次元配体三辛基膦氧化物（TOPO）进行了比较。二磷酸二氧化物（TPDPDO），双苯基（二苯基磷酸）甲烷（BDPPM）和乙烷和乙烷（BDPPE）作为双齿配体，以及Tris（Diphenylyl磷酸）甲烷（TDPPM）作为Tridentate配对的甲烷均与二离子配对的载体，这些甲烷（tdppm）与离子配对的载体均具有这些分裂的载体。被调查。发现碱性地球（Mg，CA，SR和BA）和一些二价过渡金属（Co，Ni，Cu，Zn和Cd）很容易用BDPPM或TDPPM，tDPPM以及高氯酸盐或picrate或Picrate离子提取。托普或bdppe的提取非常差。当BDPPM或TDPPM附着在金属离子上时，六元的环将形成非常稳定的环，而BDPPE则预计七元环。在BDPPM/CLO_4系统中的苯/水界面上观察到沉淀。 picrate是合适的阴离子，而不是高氯酸盐。通过图形方法获得了提取物质的组成。用1-苯基-3-甲基-4-苯甲酰基-5-吡唑酮（HPMBP）或4-三氟乙酰乙基-5-吡唑酮（HPMTFP）（HPMTFP）和磷脂的协同提取二价金属和4-三氟乙醇乙酰基-5-吡唑酮（HPMBP）和4-三氟甲基苯基-5-吡唑酮（HPMBP）。发现BDPPM比Topo和BDPPE更强大地形成配体。 TDPPM被认为是碱地球协同提取中的双齿配体。可以根据空缺配位数，中性配体允许的空间大小以及中性配体的分子结构来解释加合物形成反应的稳定性和参与反应的中性配体的数量。