Yang Zhi-Ce, Cai Hong-Xue, Bacha Raza Ullah Shah, Ding Song-Dong, Pan Qing-Jiang
Key Laboratory of Functional Inorganic Material Chemistry (Ministry of Education), School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, China.
College of Chemistry, Sichuan University, Chengdu 610064, China.
Inorg Chem. 2022 Aug 1;61(30):11715-11724. doi: 10.1021/acs.inorgchem.2c01379. Epub 2022 Jul 15.
Actinide complexes, which could enable the electrocatalytic HO reduction, are not well documented because of the fact that actinide-containing catalysts are precluded by extremely stable actinyl species. Herein, by using relativistic density functional theory calculations, the arene-anchored trivalent actinide complexes (ArO)An (marked as [AnL]) with desirable electron transport between metal and ligand arene are investigated for H production. The metal center is changed from Ac to Pu. Electron-spin density calculations reveal a two-electron oxidative process (involving high-valent intermediates) for complexes [AnL] (An = P-Pu) along the catalytic pathway. The electrons are provided by both the actinide metal and the arene ring of ligand. This is comparable to the previously reported uranium catalyst (ArO)U (Ad = adamantine and = mesitylene). From the thermodynamic and kinetic perspectives, [PaL] offers appreciably lower reaction energies for the overall catalytic cycle than other actinide complexes. Thus, the protactinium complex tends to be the most reactive for HO reduction to produce H and has the advantage of its experimental accessibility.
锕系元素配合物能够实现电催化水还原，但由于含锕系元素的催化剂会被极其稳定的锕酰物种所抑制，因此相关文献记载较少。在此，通过相对论密度泛函理论计算，研究了在金属与配体芳烃之间具有理想电子传输性能的芳烃锚定三价锕系元素配合物(ArO)An（标记为[AnL]）用于产氢。金属中心从锕(Ac)变化到钚(Pu)。电子自旋密度计算表明，配合物[AnL]（An = P - Pu）在催化途径中存在一个双电子氧化过程（涉及高价中间体）。电子由锕系金属和配体的芳烃环共同提供。这与先前报道的铀催化剂(ArO)U（Ad = 金刚烷， = 均三甲苯）情况相当。从热力学和动力学角度来看，[PaL]在整个催化循环中提供的反应能量明显低于其他锕系元素配合物。因此，镤配合物对于水还原产氢往往具有最高的反应活性，并且具有实验可及性的优势。
