Abstract

A quantitative criterion of the kinetic stabilization of unstable metal oxidation states during complexation has been proposed on the basis of the of a comparative analysis of the stability constants β_1yn and rate constants k_n = 1 of intramolecular redox decomposition of cerium(IV) complexes [CeH_yL_n]^4+y–nk with a number of aliphatic organic compounds (L = H_kR, R(OH)_k) in sulfate and nitrate media, as well as established correlations between log k_{n = 1} and log β_1yn. This criterion is defined as the relative kinetic stability of the complexes to intramolecular redox decomposition –log (k_n = 1/k⁰_{n = 1}) determined from the log k_{n = 1}–log β_1yn correlations. The latter have been found to associeted with the Nernst equation.

中文翻译：

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铈（IV）配合物与某些脂肪族有机化合物的相对动力学稳定性

摘要

不稳定的金属氧化态的络合期间动力学稳定性的定量标准已经提出的稳定常数β进行比较分析的基础上_1个炔和速率常数ķ _{Ñ  = 1}铈的分子内氧化还原分解的（IV）配合物[CeH _y L _n ] ^{4+ y – nk}与硫酸盐和硝酸盐介质中的许多脂族有机化合物（L = H _k R，R（OH）_k），以及log k _{n = 1}和log之间的已建立相关性 β _{1 YN}。该标准被定义为复合物的分子内氧化还原分解-log的相对动力学稳定性（ķ _{Ñ  = 1} / ķ ⁰ _{Ñ = 1}从日志确定）  ķ _{Ñ = 1} -logβ _1炔相关性。已发现后者与能斯特方程有关。