Characterization of molecular oxygen binding to [CoII(1,4,8,11-tetraazacyclotetradecane)] in aqueous solutions

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta Pub Date : 2024-11-07 DOI:10.1016/j.ica.2024.122437

Lu Quan Hau, Laouénan André, L’Her Maurice

引用次数: 0

Abstract

1, 4, 8,11-tetraazacyclotetradecane (cyclam), a cyclic tetramine, binds various metal cations among which Co²⁺ is of a particular importance as its complex can bind molecular oxygen and help separate it from nitrogen of air. The stability constants of the O₂ complexes have been the subject of many works but, due to kinetic complications, none of these studies yielded satisfactory results. In the present work spectrophotometry has been used to investigate the acid-base properties of the various species as well as the kinetic and thermodynamic aspects of their formation. For kinetic reasons the superoxo complex is formed primarily which then evolves to the µ-peroxo derivative, the most stable species. This study reveals why the many previous experiments conducted to measure the stability constants of the oxygen complexes have failed.

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分子氧与水溶液中[CoII(1,4,8,11-四氮杂环十四烷)]的结合特征

1,4,8,11-四氮杂环十四烷（cyclam）是一种环状四胺，可与多种金属阳离子结合，其中 Co2+ 尤为重要，因为其络合物可与分子氧结合，并有助于将分子氧从空气中的氮气中分离出来。关于 O2 复合物的稳定性常数已经有很多研究，但由于动力学上的复杂性，这些研究都没有取得令人满意的结果。在本研究中，我们使用分光光度法来研究各种物质的酸碱特性以及它们形成的动力学和热力学方面。由于动力学原因，形成的主要是超氧复合物，然后演变为 µ-peroxo 衍生物，这是最稳定的物种。这项研究揭示了以往许多测量氧络合物稳定性常数的实验失败的原因。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Inorganica Chimica Acta 化学-无机化学与核化学

CiteScore

6.00

自引率

3.60%

发文量

440

审稿时长

35 days

期刊介绍： Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews. Topics covered include: • chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies; • synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs); • reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models; • applications of inorganic compounds, metallodrugs and molecule-based materials. Papers composed primarily of structural reports will typically not be considered for publication.