Exploring acidity-dependent PCET pathways in imino-bipyridyl cobalt complexes†

IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR
Jueun Lee, Daeun Jung and Junhyeok Seo
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引用次数: 0

Abstract

The electrochemical proton reactivity of transition metal complexes has received intensive attention in catalyst research. The proton-coupled electron transfer (PCET) process, influenced by the coordination geometry, determines the catalytic reaction mechanisms. Additionally, the pKa value of a proton source, as an external factor, plays a crucial role in regulating the proton transfer step. Understanding the effects of variations in the pKa values of Brønsted acids on the PCET process is therefore essential. This study compares the PCET pathways of two high-spin cobalt (Co) complexes with contrasting exchange coupling interactions under acidic conditions with high and low pKa values. These findings reveal how proton reduction reactions in high-spin Co complexes are affected by the internal factor of the spin state, as well as an external factor related to the proton source. The corresponding reaction mechanisms are also proposed based on these observations.

Abstract Image

探索亚氨基-联吡啶基钴配合物中酸度依赖的PCET通路
过渡金属配合物的电化学质子反应性是催化剂研究的热点。质子耦合电子转移(PCET)过程受配位几何形状的影响,决定了催化反应机理。此外,质子源的pKa作为一个外部因素,在质子转移过程中起着至关重要的调节作用。因此,了解Brønsted酸的pKa变化对PCET过程的影响是必要的。本研究比较了两种高自旋钴(Co)配合物在高pKa值和低pKa值的酸性条件下具有不同交换偶联作用的PCET途径。这些发现揭示了高自旋钴配合物中质子还原反应是如何受到自旋态的内部因素和质子源相关的外部因素的影响的。并在此基础上提出了相应的反应机理。
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来源期刊
Dalton Transactions
Dalton Transactions 化学-无机化学与核化学
CiteScore
6.60
自引率
7.50%
发文量
1832
审稿时长
1.5 months
期刊介绍: Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.
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