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Quantitative Description of Reactivity of Metal Complexes and Its Application to Kinetic Analysis

金属配合物反应性的定量描述及其在动力学分析中的应用

基本信息

批准号：
13640601
负责人：
YAMADA Shinkichi
金额：
$ 1.98万
依托单位：
Shizuoka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2003
项目状态：
已结题

项目摘要

From the experimental studies to determine the electron-donor constant E(A) of some multidentate ligands A and the consideration on the effect of each donor atom involved in A on E(A), the following results were obtained.1.Using monodentate pyridines as A, the coruplexation rate of Ni(II)-A 1:1 complexes with 1,10-phenantroline(phen) was studied ; and the rate constant k_<NiA>, given by d[Ni(phen)^<2+>]/dt=k_<Ni>[Ni^<2+>][phen]+ k_<NiA>[NiA][phen], was determined. With k_<NiA> thus obtained, k_<NiA>^<-H2O>(the exchange rate constant of coordinated water molucule at NiA, and E(A) of the pyridines was estimated. From these studies, it was found that the effect of hydrophobic interaction between A and phen should be taken into account for the estimation of E(A) of the pyridines.2.Using multidentate pyridines as A, E(A) of these pyridines was estimated in the same way as monodentate pyridines. From these studies, it was found that the effective E(A) of the pyridines is given by the summation of E(X) of each donor atom X involved in A corrected for the effect of vicinal functions.3.Using phthalic acid, anthranilic acid, o-phenylenedliamine, benzoic acid and aniline as A, the effective E(A) of these ligands is estimated. From these studies, it was found that the same discussion as on pyridines was also applicable to these aromatic ligands and with this effective E(A), the basicity constant of A (H(A)), may be estimated from the correlation logK_<NiA>=αE(A)+βH(A) where K_<NiA> refers to the formation constant of NiA, and α and β are constants characteristic of nickel(II). With the same parameers, the reasonableness of the experimental conditions of our kinetic analysis proposed previously were examined.

通过测定几种多齿配体A的给电子常数E（A），并考虑A中各给电子原子对E（A）的影响，得到以下结果：1.以单齿吡啶为A，研究了Ni（Ⅱ）-A 1：1配合物与1，10-菲咯啉（phen）的共聚合反应速率，确定了速率常数k_<NiA>（d[Ni（phen）^<2+>]/dt=k_<Ni>[Ni^<2 +>][phen]+ k_<NiA>[NiA][phen]）。用此<NiA>方法计算了配<NiA><-H2O>位水分子在NiA上的交换速率常数k_1和吡啶类化合物的交换速率常数E（A）。研究发现，在计算吡啶类化合物的E（A）时，应考虑A与phen之间的疏水相互作用的影响。2.以多齿吡啶为A，采用与单齿吡啶相同的方法计算了这些吡啶类化合物的E（A）。研究结果表明，吡啶类配体的有效E（A）可以由A中每个给体原子X的E（X）之和给出，并对邻位官能团的影响进行了修正。3.以邻苯二甲酸、邻氨基苯甲酸、邻苯二胺、苯甲酸和苯胺为A，估算了这些配体的有效E（A）。从这些研究中发现，对吡啶类配体的讨论也适用于这些芳香配体，并且利用这个有效E（A），A（H（A））的碱性常数可以由相关式logK_<NiA>=αE（A）+βH（A）估算，其中K_<NiA>是NiA的形成常数，α和β是镍（II）的特征常数。在相同的参数下，考察了我们以前提出的动力学分析实验条件的合理性。