Different pentacoordinate spirophosphoranes were investigated by H/D exchange and NMR tracking experiments. The H/D exchanged site of spirophosphoranes was confirmed to be the NH bond instead of the PH bond according to the integration of the signal changes in proton-decoupled, proton-coupled ³¹P NMR and ¹H NMR tracking experiments. The reactivity of NH bond at the spiroring of spirophosphoranes was explored by the rate constant of H/D exchange of different spirophosphoranes. The results demonstrated that the reactivity of NH bond of spirophosphoranes was influenced by steric hindrance and the species of substituent at phosphorus atom, and the electronic effect of the substituent was the main effect factor on the reactivity of the NH bond. The strong electron-withdrawing group at phosphorus resulted in more reactive NH bond of spirophosphoranes. These results are beneficial to further understand and explore the characteristics of pentacoordinate spirophosphoranes.

通过H / D交换和NMR跟踪实验研究了不同的五配位螺正膦。根据质子去耦，质子耦合的³¹ P NMR和¹ H NMR跟踪实验中信号变化的积分，确认了螺磷光烷的H / D交换位点是N H键而不是P H键。通过不同螺磷光烷的H / D交换速率常数，探索了在螺磷光烷激发时NH键的反应性。结果表明，螺环磷烷的NH键的反应性受空间位阻和磷原子上取代基的种类的影响，取代基的电子效应是影响N反应性的主要因素。H键。磷处的强吸电子基团导致螺磷杂环戊烷具有更高的反应性N H键。这些结果有利于进一步理解和探索五配位螺正膦的特性。