Formate oxidation via β-deprotonation in [Ni(PR2NR′2)2(CH3CN)]2+ complexes
Formate oxidation via β-deprotonation in [Ni(PR2NR′2)2(CH3CN)]2+ complexes
复制标题
[Ni(PR2NR′2)2(CH3CN)]2+ 配合物中通过 β-去质子化作用进行甲酸氧化
DOI：
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发表时间：
2012
期刊：
影响因子：
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通讯作者：
C. Kubiak
中科院分区：
文献类型：
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作者：
Candace S. Seu;A. Appel;Michael D. Doud;D. Dubois;C. Kubiak
我们实验室最近的研究表明，最初作为人工氢化酶开发的[Ni（PR 2NR ′2）2（CH 3CN）]2+络合物也是甲酸盐氧化的活性电催化剂（TOF = 16 s−1）。目前工作的重点是开发一个详细的理解的催化机制，这将有助于设计改进的催化剂的相互转化的二氧化碳和甲酸。基于电化学和光谱实验，包括新的[Ni（PCy 2NPhOMe 2）2（CH 3CN）]2+配合物的数据，我们提出了一种机制，其中速率决定步骤是从Ni-O2 CH β-H到配体侧基的质子转移，加上2 e −转移到Ni（II），避免了直接氢化物转移到金属。
Recent studies from our laboratories have shown that the [Ni(PR2NR′2)2(CH3CN)]2+ complexes originally developed as artificial hydrogenases are also active electrocatalysts for formate oxidation (TOF ∼16 s−1). The focus of the current work is to develop a detailed understanding of the catalytic mechanism, which would aid in the design of improved catalysts for the interconversion of CO2 and formate. Based on electrochemical and spectroscopic experiments, including data for a new [Ni(PCy2NPhOMe2)2(CH3CN)]2+ complex, we propose a mechanism in which the rate-determining step is a proton transfer from the Ni–O2CH β-H to the ligand pendant base coupled with a 2e− transfer to Ni(II), circumventing direct hydride transfer to the metal.
影响因子：
2.9
作者：
Michaelis L;Menten ML;Johnson KA;Goody RS
通讯作者：
Goody RS