Ligand Protonation at Carbon, not Nitrogen, during H 2 Production with Amine-Rich Iron Electrocatalysts
Ligand Protonation at Carbon, not Nitrogen, during H 2 Production with Amine-Rich Iron Electrocatalysts
复制标题
使用富胺铁电催化剂生产 H 2 期间，配体在碳而非氮上质子化
DOI：
10.1021/acs.inorgchem.1c03142
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发表时间：
2021
影响因子：
4.6
通讯作者：
Prokopchuk, Demyan E.
中科院分区：
文献类型：
--
作者：
Sánchez, Práxedes;Goel, Bhumika;Neugebauer, Hagen;Lalancette, Roger A.;Grimme, Stefan;Hansen, Andreas;Prokopchuk, Demyan E.
我们提出了含有与铁配位的富电子三胺-环戊二烯基 (Cp) 配体的单金属制氢电催化剂。从三羰基铁前体选择性挤出 CO 后，在外源酸存在下通过循环伏安法观察电催化作用。与次级配位层中的胺在电催化过程中经常被质子化的事实相反，综合量子化学计算表明胺可能不起到质子中继的作用；相反，1e-还原后内-Cp环质子化是最有利的。这种不寻常的机制途径强调需要通过协同结合实验和理论资源来考虑 H+/e- 加成产物的广泛领域。
We present monometallic H2production electrocatalysts containing electron-rich triamine-cyclopentadienyl (Cp) ligands coordinated to iron. After selective CO extrusion from the iron tricarbonyl precursors, electrocatalysis is observed via cyclic voltammetry in the presence of an exogenous acid. Contrary to the fact that amines in the secondary coordination sphere are often protonated during electrocatalysis, comprehensive quantum-chemical calculations indicate that the amines likely do not function as proton relays; instead,endo-Cp ring protonation is most favorable after 1e–reduction. This unusual mechanistic pathway emphasizes the need to consider a broad domain of H+/e–addition products by synergistically combining experimental and theoretical resources.