Kinetics of Ligand Substitution Reaction between Cyanide Ion and NiL<sub>2</sub>(L=4-(2-Pyridylazo)resorcinol, Diethylenetriamine, and Ethylenediamine)
loss. The backward reactionbetween [Ni(CN)4]2− and L is first order in each reactant and inverse first order in cyanide. Though the mechanism for the reactions appears to be same, there are kinetic differences in the behaviour of en and the other two chelates. The rate determining step for the three reactions have been identified. The activation parameters for the forward reaction have been evaluated
氰化物离子与一些双配合物 [NiL2]2−2n 的取代反应动力学,其中 Ln− 是 4-(2-吡啶偶氮)间苯二酚、二亚乙基三胺或乙二胺,形成方形平面配合物 [Ni(CN)4] 2- 已经在水溶液中进行了分光光度法研究。速率表达式的形式为:rate=kdNiL2+k'[CN−]}[NiL22−2n],其中 k' 在 par 和 dien 情况下是复合速率常数,在 en 情况下等于 kCNNiL2。这些结果表明这些双配合物没有直接转化为 [Ni(CN)4]2- 而是首先失去一个配体分子,而氰化物有助于这种损失。[Ni(CN)4]2-和L之间的逆反应在每种反应物中都是一级反应,而在氰化物中则是逆一级反应。虽然反应的机制看起来是一样的,en 和其他两种螯合物的行为存在动力学差异。已经确定了三个反应的速率确定步骤。已经评估了正向反应的活化参数以支持...
Kinetic and spectroscopic studies with a rapid-scanning spectrometer. Part 1. Transient intermediates in the dissociation of nickel(II) polyamine complexes
作者:Terence J. Kemp、Peter Moore、Geoffrey R. Quick
DOI:10.1039/dt9790001377
日期:——
Successive stages in the acid-catalysed aquation of several polyamine chelates of NiII have been characterised both optically and kinetically by means of a rapid-scanningspectrometer. Complete spectra of several new transientintermediates are reported and assigned. When two terdentate ligands, viz. diethylenetriamine (dien), are involved it is established that one is completely removed in two stages