作者:Wee Shan Tay、Yongxin Li、Sumod A. Pullarkat、Pak-Hing Leung
DOI:10.1021/acs.organomet.9b00723
日期:2020.1.13
Secondary arsines were observed to decomplex strongly chelating phosphapalladacycles rapidly under mild conditions. As–H bond migration led to ortho-protonation of the C,P ligand. On the other hand, N–H and P–H bonds in amine and phosphine analogues were acidified under the same conditions and no ligand decomplexation of the metallacycle was observed. Subsequently, secondary arsines bearing the As–H
观察到次要的rs在温和的条件下会迅速使强螯合的磷apadacycles迅速复合。As–H键迁移导致C,P配体的原质子化。另一方面,在相同条件下,胺和膦类似物中的NH和PH键被酸化,未观察到金属环的配体分解。随后,通过定向原位金属化(DoM)和分解方法将带有As-H键的次要砷化氢用于氘化。在前者中,HAsPh 2是一种方便的氘穿梭,它促进了中性条件下DoM-Palladacycle中间体的邻位氘化。在没有专门的预制氘化剂的情况下,实现了很高的氘掺入率(> 99%)。在后者中,HAsPh 2在室温下30分钟内以95-98%的优异收率提供了Pd的单体,二聚体,二齿和三齿络合物的前体。概述了分子内As–H插入Pd–C键的关键反应步骤,并评估了区域异构对邻质子化途径的影响。