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Pt(II) complexes bearing P,N-donor ligands as catalysts in chemoselective hydrosilylation, hydrogermylation, and hydroboration of terminal alkenes
Journal of Catalysis ( IF 7.3 ) Pub Date : 2024-04-10 , DOI: 10.1016/j.jcat.2024.115494
Hanna Stachowiak-Dłużyńska , Marcin Gruszczyński , Maciej Kubicki , Grzegorz Hreczycho

In this report, we present the synthesis of six novel neutral platinum complexes employing readily available P,N-donor ligands through a straightforward two-step procedure. Subsequently, we investigated their catalytic activity in the hydroelementation of terminal olefins, highlighting their versatile utility in material and natural product chemistry. The efficient addition of silicon, germanium, and boron hydrides to the CC bond at low catalyst loading occurred exclusively in an anti-Markovnikov manner. Furthermore, our substrate scope encompasses a wide range of aliphatic and aromatic alkenes, featuring substituents with varying electronic properties. In contrast to many previous Pt-complexes, our catalytic system displayed exceptional chemoselectivity towards other unsaturated functional groups, such as carbonyl and internal CC bonds. Notably, it also exhibited remarkable tolerance to hydroxyl, alkoxyl, silyl, and thioether moieties. Additionally, we accentuated the prowess of our catalyst, showcasing its capability to sustain consistent activity and selectivity throughout numerous catalytic cycles.

中文翻译:

带有 P,N 供体配体的 Pt(II) 配合物作为末端烯烃化学选择性氢化硅烷化、氢甲酰化和硼氢化反应的催化剂

在本报告中,我们介绍了六种新型中性铂配合物的合成,使用容易获得的 P,N-供体配体,通过简单的两步程序合成。随后,我们研究了它们在末端烯烃加氢元素化中的催化活性,强调了它们在材料和天然产物化学中的多功能用途。在低催化剂负载量下,硅、锗和氢化硼仅以反马尔可夫尼科夫方式有效加成到 CC 键上。此外,我们的底物范围涵盖广泛的脂肪族和芳香族烯烃,其取代基具有不同的电子特性。与许多以前的铂配合物相比,我们的催化系统对其他不饱和官能团(例如羰基和内部 CC 键)表现出卓越的化学选择性。值得注意的是,它还表现出对羟基、烷氧基、甲硅烷基和硫醚部分的显着耐受性。此外,我们还强调了催化剂的性能,展示了其在多个催化循环中保持一致的活性和选择性的能力。
更新日期:2024-04-10
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