Electrochemical Preparation of Sm(II) Reagent Facilitated by Weakly Coordinating Anions
Electrochemical Preparation of Sm(II) Reagent Facilitated by Weakly Coordinating Anions
复制标题
弱配位阴离子促进Sm(II)试剂的电化学制备
DOI：
10.1002/chem.202301045
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
See, Kimberly A.
中科院分区：
文献类型：
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作者：
Ware, Skyler D.;Zhang, Wendy;Charboneau, David J.;Klein, Channing K.;Reisman, Sarah E.;See, Kimberly A.
二碘化钐（SmI 2）被广泛用作强单电子还原剂，通常用于在复杂体系中形成C-C键。尽管SmI 2及其相关盐具有实用性，但它们存在一些缺点，使得在大规模合成中使用Sm还原剂不切实际。在这里，我们报告的影响因素的电化学还原Sm（III）的Sm（II），对电催化Sm（III）还原的目标。我们探讨了支持电解质，电极材料，和Sm前体对Sm（II）/（III）的氧化还原和Sm物种的还原能力的影响。我们发现，抗衡离子的Sm盐的配位强度影响的可逆性和氧化还原电位的Sm（II）/（III）对，并建立抗衡离子主要决定Sm（III）的还原。在概念验证反应中，电化学生成的SmI 2与商业SmI 2溶液的性能相似。这些结果将为促进Sm-电催化反应的发展提供基本的见解。
Samarium diiodide (SmI2) is widely used as a strong one‐electron reducing agent and is often employed to form C−C bonds in complex systems. Despite their utility, SmI2and related salts suffer from several drawbacks that render the use of Sm reducing agents in large‐scale synthesis impractical. Here, we report factors influencing the electrochemical reduction of Sm(III) to Sm(II), towards the goal of electrocatalytic Sm(III) reduction. We probe the effect of supporting electrolyte, electrode material, and Sm precursor on Sm(II)/(III) redox and on the reducing power of the Sm species. We find that the coordination strength of the counteranion of the Sm salt affects the reversibility and redox potential of the Sm(II)/(III) couple and establish that the counteranion primarily determines the reducibility of Sm(III). Electrochemically generated SmI2performs similarly to commercial SmI2solutions in a proof‐of‐concept reaction. The results will provide fundamental insight to facilitate the development of Sm‐electrocatalytic reactions.