Molecular Design of Highly Selective Ligand Controlling the Geometry of the Donating Atoms

控制供体原子几何形状的高选择性配体的分子设计

• 批准号: 07640803
• 负责人: UMETANI Shigeo
• 金额: $ 1.22万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07640803/
• 关键词: Molecular Design; Ligand; Separation; Solvent Extraction; Selectivity; Aluminum; Gallium; Indium; 希土類

Studies on the solvent extraction with the modified beta-diketones revealed that the complexations of group 13 metals depend on the bite size (O-O distance in the chelate ring) and the interligand contact in the complex. The O-O distance in the In complex is one of the longest and the complexation of In is disturbed by the substituent at the alpha-position of beta-diketone, which prevents the bite size from widening to fit the structure of the complex. The complexation of Al was found to be under the great influence of the interligand contact due to its remarkably small ionic radius. The extraction is lowered by the bulky terminal substituents. Highly selective ligands for group 13 metals have been successfully designed taking the two factors into consideration.Five 1-phenyl-3-methyl-4-acyl-5-pyrazolone derivatives have been prepared. Being derived from the five membered heterocyclic 5-pyrazolone, the O-O distances of the acylpyrazolone derivatives are confirmed to be longer than those … More of the conventional beta-diketones by the semiempirical MNDO/H calculations. Owing to their long O-O distances, the extraction of In was not disturbed and made at pH 1-2. The extraction of Al was made in the higher pH region, although its ionic radius is much smaller than that of In. Considering that the acylpyrazolones are bulky and their acidities are quite similar, it is clear that the extraction of Al is under the effect of the interligand contact. The extraction reduces as the substituent at the 4-position becomes bulkier. The quantitative separation of Al from In can be achieved with the naphthoylpyrazolones. The extraction of In does not depend on the size of the substituents. The effect of the interligand contact is also seen in the extraction of Ga. The extraction is similar to that of In and decreases as the substituents becomes bulkier. Owing to the steric repulsion between the 4-pivaloyl and 3-methyl groups, the O-O distance of pivaloylpyrazolone is narrowed and the extraction of In comes close to that of Al, resulting in a quantitative separation of Ga from Al and In. Less

对修改的β-二酮溶液提取的研究表明，第13金属的络合物取决于咬合的尺寸（樱桃环中的O-O距离）和络合物中的同生接触。 IN复合物中的O-O距离是最长的O-O距离之一，IN的络合受到β-黎酮α位置的替代的影响，β-黎酮的alpha-tosition可以防止咬合的大小从宽度到适合复合物的结构。由于其极小的离子半径很小，因此发现AL的络合物受到料理接触的巨大影响。提取被大量的末端替代物降低。为了考虑这两个因素，已成功设计了第13个金属的高度选择性配体。Five1-苯基-3-甲基-4-酰基-5- 5-吡唑酮衍生物已经制备了。酰基吡唑酮衍生物的O-O距离源自五个成员的杂环5-吡唑酮，证实比那些半经验的MNDO/H计算更长。由于它们的长O-O距离，IN的提取不受影响，并在pH 1-2处进行。 Al的提取是在较高的pH区域进行的，尽管其离子半径远小于IN。考虑到酰基吡唑酮很大并且它们的酸度非常相似，很明显，Al的提取是在料理接触的效果下。随着4位处的子量的较大，提取会减少。可以使用腹泻吡唑酮来实现Al IN的定量分离。 IN的提取不取决于子登录的大小。在提取GA的提取中也可以看到料理接触的效果。随着子识别的较大，提取与IN和下降的效果相似。由于4-甲基和3-甲基之间的空间排斥，pivaloylpyrazolone的O-O距离被狭窄，并且提取In接近Al，从而导致GA与Al和IN的定量分离。较少的

项目成果

Q.T.H.Le: "Decisive Role of the Phenyl Group at the α-Position of Benzoylacetone in the Solvent Extraction of Al^<3+> and In^<3+>" J.Chem.Soc., Chem.Commun.2271-2272 (1995)

Q.T.H.Le：“苯甲酰丙酮 α 位上的苯基在 Al^<3+> 和 In^<3+> 溶剂萃取中的决定性作用”J.Chem.Soc.，Chem.Commun.2271-2272 (1995)

Z.Wei: "Synthesis, Characterization and Crystal Structure on a Mixed Ligand Complex of Aquatris (3-phenyl-4-benzoyl-5-isoxazolone)(ethanol) Europiu Monohydrate [Eu (PBI)_3(C_2H_5OH)(H_2O)]H_2O" Chem.J.Chinese Univ.16. 172-175 (1995)

Z.Wei：“Aquatris (3-苯基-4-苯甲酰基-5-异恶唑酮)(乙醇) Europiu 一水合物的混合配体配合物的合成、表征和晶体结构 [Eu (PBI)_3(C_2H_5OH)(H_2O)]H_2O

S.Tsurubou, M.Mizutani, Y.Kadota, T.Yamamoto, S.Umetani, T.Sasaki, Q.T.H.Le and M.Matsui: "Improved Extraction-Separation of Alkaline Earths and Lanthanides Using Crown Ethers as Ion Size Selective Masking Reagents : A Novel Macrocycle Application" Anal.C

S.Tsurubou、M.Mizutani、Y.Kadota、T.Yamamoto、S.Umetani、T.Sasaki、Q.T.H.Le 和 M.Matsui：“使用冠醚作为离子尺寸选择性掩蔽试剂改进碱土金属和镧系元素的萃取分离

Q. T. H. Le: "Decisive Role of the Phenyl Group at the a-Position of Benzoylacetone in the Solvent Extraction of Al^<3+> and In^<3+>" J. Chem. Soc., Chem. Commun.2271-2272 (1995)

Q. T. H. Le：“苯甲酰丙酮α位上的苯基在Al^<3>和In^<3>溶剂萃取中的决定性作用”J. Chem。

Q.T.H.Le, S.Umetani, T.Sasaki and M.Matsui: "A Highly Acidic Extractant, 4-Benzoyl-3-phenyl-5-isoxazolone : The Synergistic Extractoin of Alkaline Earths Combined with Trioctylphosphine Oxide or Bis (diphenyl-phosphinyl) methane" Bull.Chem.Soc.Japan. 68.

Q.T.H.Le、S.Umetani、T.Sasaki 和 M.Matsui：“高酸性萃取剂 4-苯甲酰基-3-苯基-5-异恶唑酮：与三辛基氧化膦或双（二苯基膦基）结合的碱土金属的协同萃取