Studies on Polydentate Organic Phosphorus Compounds as Extraction Reagents.

本文合成了以下几种多齿氧化膦，并与单齿配体三辛基氧化膦（TOPO）进行了比较，探讨了它们作为萃取试剂的可能性。四苯基二硫化氢（TPDPDO）、二（二苯基膦基）甲烷（BDPPM）和乙烷（BDPPE）为双齿配体，三（二苯基膦基）甲烷（TDPPM）为三齿配体。研究了用这些磷化氢氧化物和一个体积较大的阴离子对萃取二价金属的离子对。结果表明，用BDPPM或TDPPM和高氯酸盐或苦味酸离子可以很容易地提取出碱土（Mg、Ca、Sr和Ba）和一些二价过渡金属（Co、Ni、Cu、Zn和Cd）。TOPO或BDPPE的提取效果很差。当BDPPM或TDPPM附着在金属离子上时，六元环是非常稳定的，而BDPPE则会形成七元环。在BDPPM/ClO_4体系中，在苯/水界面处观察到沉淀。苦味酸是一种合适的阴离子，而不是高氯酸盐。用图解法得到了各提取种的成分。研究了1-苯基-3-甲基-4-苯甲酰-5-吡唑啉酮（HPMBP）或4-三氟乙酰基-5-吡唑啉酮（HPMTFP）与氧化膦的协同萃取二价金属。BDPPM是一种比TOPO和BDPPE更强的加合物形成配体。TDPPM被认为是一种双齿配体，在碱土的协同萃取中起作用。加合物形成反应的稳定性和参与反应的中性配体的数量可以用空位配位数、中性配体允许的空间大小和中性配体的分子结构来解释。

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.