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

通过对某些多齿配体A的电子给体常数E(A)的实验研究，并考虑到A所涉及的每个给体原子对E(A)的影响，得到如下结果：以单齿吡啶为A，研究了Ni(II)-A 1:1配合物与1,10-吩啉（phen）的偶配速率；得到了反应速率常数k_<NiA>，即d[Ni(phen)^<2+>]/dt=k_<Ni>[Ni^<2+>][phen]+ k_<NiA>[NiA][phen]。得到k_<NiA>, k_<NiA>^<-H2O>（配位水分子在NiA处的交换速率常数），并计算了吡啶的E(A)。从这些研究中发现，在估计吡啶的E(A)时，应考虑到A与phen之间疏水相互作用的影响。用多齿吡啶作为A，用与单齿吡啶相同的方法估计了这些吡啶的E(A)。从这些研究中发现，吡啶的有效E(A)是由A中涉及的每个给体原子X的E(X)的总和给出的，并对邻函数的影响进行了修正。以邻苯二甲酸、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，与吡啶上的讨论相同，也适用于这些芳香配体，利用有效E(A)，可以由相关logK_<NiA>=αE(A)+βH(A)来估计A （H(A)）的碱度常数，其中K_<NiA>为NiA的形成常数，α和β为镍（II）的特征常数。在相同的参数下，检验了我们先前提出的动力学分析实验条件的合理性。

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.