Koner Abhishek, Morgenstern Bernd, Andrada Diego M
Faculty of Natural Sciences and Technology, Department of Chemistry, Saarland University, Campus C4.1, 66123, Saarbrücken, Germany.
Angew Chem Int Ed Engl. 2022 Aug 1;61(31):e202203345. doi: 10.1002/anie.202203345. Epub 2022 Jun 23.
The BP unsaturated unit is a very attractive functional group as it provides novel reactivity and unique physical properties. Nonetheless, applications remain limited so far due to the bulky nature of B/P-protecting groups, required to prevent oligomerization. Herein, we report the synthesis and isolation of a N-heterocyclic carbene (NHC)-stabilized phosphaborene, bearing a trimethylsilyl (TMS) functionality at the P-terminal, as a room-temperature-stable crystalline solid accessible via facile NHC-induced trimethylsilyl chloride (TMSCl) elimination from its phosphinoborane precursor. This phosphaborene compound, bearing a genuine B=P bond, exhibits a remarkable ability for undergoing P-centre metathesis reactions, which allows the isolation of a series of unprecedented phosphaborenes. X-ray crystallographic analysis, UV/Vis spectroscopy, and DFT calculations provide insights into the B=P bonding situation.
硼磷不饱和单元是一个非常有吸引力的官能团，因为它具有新颖的反应活性和独特的物理性质。然而，由于防止低聚所需的硼/磷保护基团体积庞大，迄今为止其应用仍然有限。在此，我们报道了一种N-杂环卡宾（NHC）稳定的磷硼烯的合成与分离，该磷硼烯在P端带有三甲基硅基（TMS）官能团，是一种室温稳定的结晶固体，可通过NHC诱导其膦硼烷前体中的三甲基氯硅烷（TMSCl）消除反应轻松获得。这种具有真正B=P键的磷硼烯化合物表现出进行P中心复分解反应的显著能力，这使得一系列前所未有的磷硼烯得以分离。X射线晶体学分析、紫外/可见光谱和密度泛函理论计算为B=P键合情况提供了深入见解。
