X = pseudohalogen = CN, N3, NCO, NCS, and PCO) utilizing a phosphorus-centered cyclic biradicaloid, [P(μ-NTer)]2, is reported. These formal Brønsted acids were generated in situ as gases and passed over the trapping reagent, the biradicaloid [P(μ-NTer)]2, leading to the formation of the addition product [HP(μ-NTer)2PX] (successful for X = CN, N3, and NCO). In addition to this direct addition reaction
据报道,利用以
磷为中心的环状双自由基,[P(μ-NTer)] 2捕集经典的拟卤化氢(HX,X =拟卤素= CN,N 3,NCO,
NCS和
PCO)。这些形式的布朗斯台德酸作为气体原位产生,并通过捕集剂双自由基[P(μ-NTer)] 2,导致形成加成产物[HP(μ-NTer)2 PX]( X = CN,N 3和NCO)。除了这种直接加成反应之外,还应用了两步过程,因为我们未能分离出H
PCO和H
NCS加成产物。此两步过程包括生成和分离高反应性[HP(μ-NTer)2 PX]+阳离子作为[B(C 6 F 5) 4 ] -盐,然后与诸如[cat] X(cat = PPh 4, n -Bu 3 NMe)的盐进行盐复分解,这也会得到所需的[HP( μ-NTER) 2 PX]的产品,与
PCO中的反应除外-盐。在这种情况下,观察到质子迁移,最终形成[3.1.1]-异
丙炔型笼状化合物,即H
PCO加合物的OC(