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

对改性β -二酮的溶剂萃取研究表明，13族金属的配合物取决于配合物的咬合大小（螯合环上的O-O距离）和配体间的接触。in配合物的O-O距离是最长的之一，并且在-二酮的α位置上的取代基干扰了in的配位，阻止了咬合尺寸的扩大以适应配合物的结构。由于Al的离子半径非常小，其配体间的接触对其络合作用有很大的影响。大量的末端取代基降低了萃取。考虑到这两个因素，已经成功地设计了13族金属的高选择性配体。制备了5个1-苯基-3-甲基-4-酰基-5-吡唑酮衍生物。由五元杂环5-吡唑酮衍生而来的酰基吡唑酮衍生物，通过半经验MNDO/H计算证实其O-O距离比传统的β -二酮更长。由于它们的O-O距离较长，因此在pH 1-2的条件下不影响In的提取。虽然Al的离子半径比in小得多，但在较高的pH区域进行了萃取。考虑到酰基吡唑啉酮体积大且酸度相近，很明显，Al的提取是受配体间接触的影响。随着4位取代基体积增大，萃取量减小。采用萘基吡唑酮可以实现铝和铟的定量分离。In的萃取不取决于取代基的大小。配体间接触的影响也见于Ga的提取。萃取过程与In相似，随取代基体积增大而减小。由于4-戊酰基和3-甲基之间的空间排斥作用，戊酰吡唑酮的O-O距离被缩小，提取的In接近于提取的Al，从而定量分离了Ga与Al和In。少

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

S.Tsurubou: "Improved Extraction-Separation of Alkaline Earths and Lanthanides Using Crown Ethers as Ion Size Selective Masking Reagents : A Novel Macrocycle Application" Anal.Chem.67. 1465-1469 (1995)

S.Tsurubou：“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：一种新颖的大环应用”Anal.Chem.67。

Q.T.H.Le, S.Umetani, M.Suzuki and M.Matsui: "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、S.Umetani、M.Suzuki 和 M.Matsui：“苯甲酰丙酮 a 位上的苯基在 Al^<3 > 和 In^<3 > 溶剂萃取中的决定性作用”J.Chem。