Thermodynamic and Structural Studies of Metal Complexes in Solution and its Application to Analytical Chemistry

溶液中金属配合物的热力学和结构研究及其在分析化学中的应用

• 批准号: 06453066
• 负责人: KAWASHIMA Takuji
• 金额: $ 4.54万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06453066/
• 关键词: Thermodynamic parameter; Structure of Metal Complexes in Solution; Redox reaction; Catalytic effect; Activator; Flow-injection Analysis; 錯形成の熱力学的パラメーター

Complexation of pyridine (py), 3-methylpyridine (3Me-py) and 4-methylpyridine (4Me-py) with bivalent transition metal ions has been investigated by calorimetry and spectrophotometry in N,N-dimethylformamide (DMF) and acetonitrile (MeCN). It was revealed that the structure of the [ML_4] ^<2+> complexes (M=Co, Ni, Cu) is octahedral, while that of the [ZnL_4] ^<2+> complex is tetrahedral. This is consistent with our EXAFS (extended X-ray absorption fine structure) measurements showing that the solvation structure of the manganese (II), coblt (II) and nickel (II) ions is six-coordinate octahedral in 4Me-py and 3Me-py, while that of the zinc (II) ion is four-coordinate tetrahedral in 4Me-py. Complexation of 18-crown-6 with alkali-metal, alkaline earth metal and ammonium ions in various aprotic solvents and water has been investigated by titration calorimetry. The complexation of 18-crown-6 is more favorable in the aprotic solvents than in water. The reaction enthalpies and entropies, howeve … More r, differ much among the solvents. Thus the complexation of 18-crown-6 reflects the different solvation of 18-crown-6 and also the different degree of solvent strucutre. Complexation of 18-crown-6 with alkaline earth metal ions in DMF-MeCN mixtures has also been investigated by calorimetry and it was indicated that the metal ions are preferentially solvated with DMF molecules and 18-crown-6 is preferentially solvated with MeCN molecules in DMF-MeCN mixtures.A spectrophotometric method was developed for the determination of ultratrace amounts of copper (II) based on its catalytic effect on the oxidative coupling reaction of 3-methyl-2-benzothiazolinone hydrazone with N-ethyl-N- (2-hydroxy-3-sulfopropyl) -3,5-dimethoxyaniline to produce an intensely colored dye in the presence of hydrogen peroxide. In this reaction, pyridine acted as an effective activator for the catalysis of copper (II). A flow injection analysis (FIA) method was developed for the simultaneous determinations of vanadium (V) -vanadium (IV), of iron (III)-vanadium (V) and of iron (III) -chromium (VI) using a single injection. In the presence of 1,10-phenanthroline (phen), iron (III) is easily reduced by vanadium (IV) to iron (II), followed by the formation of a red iron (II) -phen complex (lambda_<max>=510 nm), which shows a positive FIA peak corresponding to the concentration of iron (III). On the other hand, in the presence of diphosphate reductions of vanadium (V) and/or chromium (VI) with iron (II) occur easily and a negative FIA peak at 510nm corresponding to the concentration of vanadium (V) and/or chromium (VI) is obtained. Less

用量热法和分光光度法研究了吡啶（py）、3-甲基吡啶（3 Me-py）和4-甲基吡啶（4 Me-py）在N，N-二甲基甲酰胺（DMF）和乙腈（MeCN）中与二价过渡金属离子的络合作用。结果表明，[ML_4] ^<2+>配合物（M=Co，Ni，Cu）的结构为八面体，而[ZnL_4] ^<2+>配合物的结构为四面体。这与我们的EXAFS（扩展X射线吸收精细结构）测量结果一致，表明锰（II）、钴（II）和镍（II）离子在4 Me-py和3 Me-py中的溶剂化结构为六配位八面体，而锌（II）离子在4 Me-py中的溶剂化结构为四配位四面体。本文用滴定量热法研究了18-冠-6与碱金属、碱土金属和铵离子在各种非质子溶剂和水中的络合反应。18-冠-6在非质子溶剂中的络合作用比在水中更有利。然而， ...更多信息 r，在溶剂之间差别很大。因此，18-冠-6的络合反应反映了18-冠-6的不同溶剂化作用和不同程度的溶剂结构。用量热法研究了在DMF-MeCN混合溶剂中18-冠-6与碱土金属离子的络合作用，发现在DMF-MeCN混合溶剂中，金属离子优先与DMF分子溶剂化，18-冠-6优先与MeCN分子溶剂化。基于其对在过氧化氢存在下3-甲基-2-苯并噻唑啉酮腙与N-乙基-N-（2-羟基-3-磺丙基）-3，5-二甲氧基苯胺的氧化偶联反应产生强烈着色染料的催化作用。在该反应中，吡啶作为铜（II）催化的有效活化剂。本文建立了一种流动注射分析方法，可一次进样同时测定钒（V）-钒（IV）、铁（III）-钒（V）和铁（III）-铬（VI）。在1，10-邻菲咯啉（phen）存在下，Fe（III）易被钒（IV）还原为Fe（II），形成红色的Fe（II）-phen络合物（λ <max>=510 nm），该络合物具有与Fe（III）浓度相对应的FIA正峰。另一方面，在二磷酸盐存在下，钒（V）和/或铬（VI）容易被铁（II）还原，并且在510 nm处获得对应于钒（V）和/或铬（VI）浓度的负FIA峰。少

项目成果

K.Ozutsumi: "Structure of the Monohalogenocadmium (II) Complexes in N,N-Dimethylformamide" J.Mol.Liquids. 65/66. 361 (1995)

K.Ozutsumi：“N,N-二甲基甲酰胺中单卤镉 (II) 配合物的结构”J.Mol.Liquids。

N.Teshima, K.Ayukawa, T.Kawashima: "Simultaneous flow injection determination of iron (III) and vanadium (V) and of iron (III) and chromium (VI) based on redox reactions" Talanta. 43. 1755 (1996)

N.Teshima、K.Ayukawa、T.Kawashima：“基于氧化还原反应同时流动注射测定铁 (III) 和钒 (V) 以及铁 (III) 和铬 (VI)”Talanta。

Norio Teshima: "Effect of 2,2'-bipyridine and 1,10-phenanthroline on the redox reaction of metal ions and its application to potentiometric titrations of vanadium (IV)…" Bulletin of the Chemical Society of Japan. 69. 1975-1979 (1996)

Norio Teshima：“2,2-联吡啶和 1,10-菲咯啉对金属离子氧化还原反应的影响及其在钒 (IV) 电位滴定中的应用……”日本化学学会公报 69。1975-。 1979 (1996)

M.Kurihara, K.Ozutsumi, T.Kawashima: "Complexation of the zinc (II) iom with 2,2'-bipyridine and 1,10-phenathroline in 4-methylpyridine and solvation structure of the manganese (II), cobalt (II), nickel (II) and zinc (II) ions in 4-methylpyridine and 3-me

M.Kurihara、K.Ozutsumi、T.Kawashima：“锌 (II) 离子与 2​​,2-联吡啶和 1,10-菲咯啉在 4-甲基吡啶中的络合以及锰 (II)、钴 (

K.Ohtsu, T.Kawashima, K.Ozutsumi: "Complexation of sodium, potassium, rubidium, cesium and ammonium ions with 12-crown-4 in N,N-dimethylformamide and water" Anal.Sci.12. 37 (1996)

K.Ohtsu、T.Kawashima、K.Ozutsumi：“钠、钾、铷、铯和铵离子与 12-crown-4 在 N,N-二甲基甲酰胺和水中的络合”Anal.Sci.12。