以色列特拉维夫大学教授Dobrovetsky, Roman团队报道了单磷中心的氢分裂及其在加氢中的应用。相关研究成果于2024年6月27日发表在国际顶尖学术期刊《自然—化学》。

催化过程主要由过渡金属配合物主导。能够模拟过渡金属配合物行为的主族化合物由于其在催化中取代或补充过渡金属的潜力而引起人们的极大兴趣。虽然一些主要基团的分子中心被证明可以通过氧化加成过程活化二氢，但使用这些物种的催化氢化仍然具有挑战性。

该文中，研究人员报道了用2,6-双（邻卡波诺）吡啶钳型配体合成、分离和完全表征几何约束的磷阳离子。值得注意的是，该阳离子可以通过氧化加成到单个P_III阳离子中心来激活H–H键，产生二氢鏻阳离子。该磷阳离子还能够催化C=C双键和稠合芳族体系的氢化反应，使其成为既能在单分子主基团中心活化H₂又可用于催化氢化的主基团化合物。

该发现显示了主族化合物，特别是磷基化合物，用作金属模拟加氢催化剂的潜力。

附：英文原文

Title: Hydrogen splitting at a single phosphorus centre and its use for hydrogenation

Author: Bawari, Deependra, Toami, Donia, Jaiswal, Kuldeep, Dobrovetsky, Roman

Issue&Volume: 2024-06-27

Abstract: Catalytic processes are largely dominated by transition-metal complexes. Main-group compounds that can mimic the behaviour of the transition-metal complexes are of great interest due to their potential to substitute or complement transition metals in catalysis. While a few main-group molecular centres were shown to activate dihydrogen via the oxidative addition process, catalytic hydrogenation using these species has remained challenging. Here we report the synthesis, isolation and full characterization of the geometrically constrained phosphenium cation with the 2,6-bis(o-carborano)pyridine pincer-type ligand. Notably, this cation can activate the H–H bond by oxidative addition to a single PIII cationic centre, producing a dihydrophosphonium cation. This phosphenium cation is also capable of catalysing hydrogenation reactions of C=C double bonds and fused aromatic systems, making it a main-group compound that can both activate H2 at a single molecular main-group centre and be used for catalytic hydrogenation. This finding shows the potential of main-group compounds, in particular phosphorus-based compounds, to serve as metallomimetic hydrogenation catalysts.

DOI: 10.1038/s41557-024-01569-y

Source: https://www.nature.com/articles/s41557-024-01569-y