Structural and mechanistic studies of co-ordination compounds. Part II. Preparation, aquation, and base hydrolysis of trans-chloronitro- and trans-bromonitro-tetra-amminecobalt(III) cations

C. Poon, H. Tong
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引用次数: 4

Abstract

The preparation and characterization of trans-[Co(NH3)4NO2Cl]+ and trans-[Co(NH3)4NO2Br]+ cations are described. The assignment of geometric configuration is based on 1H n.m.r. spectroscopy. The kinetics of the aquation and base hydrolysis of these two complex cations have been studied over a range of temperature. The first-order aquation rate constants are greater than those of the corresponding bis(ethylenediamine) and 1,4,8,11-tetra-azacyclotetradecane complexes, whereas the second-order base hydrolysis rate constants are less. These results are consistent with the kinetic nephelauxetic effect of these amine ligands on the central cobalt(III) ion. Unimolecular reaction mechanisms are assigned to these reactions.
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配位化合物的结构和机理研究。第二部分。反氯硝基和反溴四胺钴(III)阳离子的制备、水化和碱水解
介绍了反式[Co(NH3)4NO2Cl]+和反式[Co(NH3)4NO2Br]+阳离子的制备和表征。几何构型的分配是基于1H核磁共振光谱。在一定温度范围内研究了这两种络合阳离子的水化和碱水解动力学。一阶水解速率常数大于二乙二胺和1,4,8,11-四氮杂环十四烷配合物的水解速率常数,而二阶碱水解速率常数较小。这些结果与这些胺配体对中心钴(III)离子的动力学抑制作用一致。这些反应都有单分子反应机理。
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