Contributions of Solute-Solvent Interactions to Ion Selectivity of Macrocyclic Ligands

溶质-溶剂相互作用对大环配体离子选择性的贡献

• 批准号: 15550062
• 负责人: KATSUTA Shoichi
• 金额: $ 2.5万
• 依托单位: Chiba University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550062/
• 关键词: Complex Stability Constants; Transfer Activity Coefficients; Alkali Metal Ion s; Crown Ethers; Selectivity; Solvent Effects; Solute-Solvent Interactions

Stability constants of 1:1 complexes of dibenzo-3m-crown-m(m=6,7,8,10) with alkali metal ions (Na^+,K^+,Rb^+,Cs^+) have been determined at 25℃ in water, nitromethane, and a few nonaqueous solvents by capillary electrophoresis or conductometry. The selectivities of these crown ethers in acetonitrile, propylene carbonate, methanol, N,N-dimethylformamide and water often obey cavity-size/ion-size relationship. On the other hand, the stability constants in nitromethane, which has the weakest solvation power for the metal ions, decrease with increasing ionic size (Na^+>K^+>Rb^+>Cs^+), reflecting the gas-phase selectivity governed by the electrostatic interaction between the ether oxygen atoms and the metal ion. It follows from this that the selectivities of these crown ethers in the solvents other than nitromethane are largely due to the solute-solvent interactions. The transfer activity coefficients of the crown ethers and their alkali metal ion complexes from nitromethane to the other polar solvents have been determined to evaluate the solvation of these solutes. It is shown that the crown ethers shields the alkali metal ions effectively from the solvents; the shielding is generally more effective for the larger crown ether. The solvent effects on the selectivities of the crown ethers are attributed to the solvation of the free metal ions.

用毛细管电泳或电导法测定了二苯并-3m-crown-m（m=6,7,8,10）与碱金属离子（Na^+,K^+,Rb^+,Cs^+）在25℃下在水、硝基甲烷和几种非水溶剂中的1:1配合物的稳定性常数。这些冠醚在乙腈、碳酸丙烯酯、甲醇、N、N-二甲基甲酰胺和水中的选择性通常服从空腔尺寸/离子尺寸的关系。另一方面，对金属离子溶剂化能力最弱的硝基甲烷的稳定常数随着离子尺寸（Na^+>K^+>Rb^+>Cs^+）的增大而减小，反映了醚氧原子与金属离子之间静电相互作用所控制的气相选择性。由此可见，除硝基甲烷外，这些冠醚在溶剂中的选择性很大程度上是由于溶质-溶剂相互作用。测定了冠醚及其碱金属离子配合物从硝基甲烷到其他极性溶剂的转移活度系数，以评价这些溶质的溶剂化作用。结果表明，冠醚有效地屏蔽了碱金属离子与溶剂的接触；对于较大的冠醚，屏蔽通常更有效。溶剂对冠醚选择性的影响归因于游离金属离子的溶剂化。

项目成果

Transfer activity coefficients of crown ethers and their alkali metal ion complexes between water and polar nonaqueous solvents(Japanese)

冠醚及其碱金属离子配合物在水与极性非水溶剂之间的转移活度系数（日文）

• 发表时间: 2003
• 期刊: Bunseki Kagaku 52(2)
• 作者: M.Tominaga;K.Suzuki;M.Kawano;T.Kusukawa;T.Ozeki;S.Sakamoto;K.Yamaguchi;M.Fujita;Shoichi Katsuta
• 通讯作者: Shoichi Katsuta

Stabilities and transfer activity coefficients from water to polar nonaqueous solvents of 1,2-bis[2-(2-methoxyethoxy)ethoxy]benzene- and benzo-18-crown-6-cation complexes

1,2-双[2-(2-甲氧基乙氧基)乙氧基]苯和苯并-18-冠-6-阳离子配合物从水到极性非水溶剂的稳定性和转移活性系数

• 发表时间: 2005
• 期刊: Journal of Coordination Chemistry 58・4
• 作者: Shoichi Katsuta;Yasuyuki Takeda;Shoichi Katsuta;Yasuyuki Takeda
• 通讯作者: Yasuyuki Takeda

Stabilities in nitromethane of alkali metal ion complexes with dibenzo-18-crown-6 dibenzo-24-crown-8 and their transfer from nitromethane to other polar solvents

碱金属离子与二苯并-18-冠-6二苯并-24-冠-8配合物在硝基甲烷中的稳定性及其从硝基甲烷到其他极性溶剂的转移

• 发表时间: 2004
• 期刊: Inorganica Chimica Acta 357・2
• 作者: M.Tominaga;K.Suzuki;M.Kawano;T.Kusukawa;T.Ozeki;S.Sakamoto;K.Yamaguchi;M.Fujita;Shoichi Katsuta
• 通讯作者: Shoichi Katsuta

Stabilities in nitromethane of alkali metal ion complexes with dibenzo-18-crown-6 and dibenzo-24-crown-8 and their transfer from nitromethane to other polar solvents

碱金属离子与二苯并-18-冠-6和二苯并-24-冠-8配合物在硝基甲烷中的稳定性及其从硝基甲烷到其他极性溶剂的转移

• 发表时间: 2004
• 期刊: Inorganica Chimica Acta 357(2)
• 作者: T.Honjo;K.Z.Hossain;C.T.Camagong;Shoichi Katsuta
• 通讯作者: Shoichi Katsuta

Shoichi Katsuta: "Stabilities in nitromethane of alkali metal ion complexes with dibenzo-18-crown-6 and dibenzo-24-crown-8 and their transfer from nitromethane to other polar solvents"Inorganica Chimica Acta. 357・2. 541-547 (2004)

Shoichi Katsuta：“碱金属离子与二苯并-18-冠-6和二苯并-24-冠-8配合物在硝基甲烷中的稳定性及其从硝基甲烷到其他极性溶剂的转移”Inorganica Chimica Acta 357・2。 2004）