Abstract

The article primarily highlights the electrocatalytic activity towards proton reduction of macrocyclic tetranuclear iron complexes [Fe₂(μ-S(CH₂)_nS-μ)(CO)₆]₂ (n = 4, 1 and n = 6, 2) with both acetic acid and trifluoroacetic acid as proton sources. Further, the electrochemical results have been compared with the analogous pentanedithiolate-bridged tetranuclear complex, [Fe₂(μ-S(CH₂)₅S-μ)(CO)₆]₂ A. The turnover frequency (TOF, acetic acid) for complexes 1 and 2 was found to be 5.7 h⁻¹ and 9.1 h⁻¹, respectively. An ECEC catalytic cycle (acetic acid) has been proposed for the tetranuclear iron complexes based on the experimental data and known literature.

Graphic abstract

The article primarily highlights the electrocatalytic activity towards proton reduction for macrocyclic tetranuclear iron complexes [Fe₂(μ-S(CH₂)₆S-μ)(CO)₆]₂, (n = 4 and 6) 1 and 2. Further comparisons have been made with the analogous pentanedithiolate-bridged complex, [Fe₂(μ-S(CH₂)₅S-μ)(CO)₆]₂ A. The influence on electrochemical properties was noted with an increase in chain length of the dithiols from n = 4 to 6 in the macrocyclic complexes, which is supported by both cyclic voltammetry and bulk electrolysis measurements.

中文翻译：

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大环蝶形铁簇复合物：电化学研究

摘要

的制品主要突出了对质子还原的大环四核铁络合物的电催化活性的[Fe ₂（μ-S（CH ₂）_ñ S-μ）（CO）₆ ] ₂（N = 4，1和n = 6，2）以乙酸和三氟乙酸为质子源。此外，电化学结果已与比较类似pentanedithiolate桥连四核配合物，的[Fe ₂（μ-S（CH ₂）₅ S-μ）（CO）₆ ] ₂ 甲。配合物1和1的周转频率（TOF，乙酸）发现2分别为5.7h ^-1和9.1h ^-1。基于实验数据和已知文献，已经提出了四核铁配合物的ECEC催化循环（乙酸）。

图形摘要

的制品主要突出了对质子还原为大环四核铁络合物的[Fe的电催化活性₂（μ-S（CH ₂）₆ S-μ）（CO）₆ ] ₂，（N = 4和6）1和2。进一步的比较已经进行了与类似pentanedithiolate桥连络合物，[铁₂（μ-S（CH ₂）₅ S-μ）（CO）₆ ] ₂ 甲。在大环配合物中二硫醇的链长从n = 4增加到6时，注意到了对电化学性能的影响，这由循环伏安法和本体电解测量法共同支持。