Pnictogen Interactions with Nitrogen Acceptors
Pnictogen Interactions with Nitrogen Acceptors
复制标题
氮元素与氮受体的相互作用
DOI：
10.1002/anie.202304960
复制
发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Shimizu, Ken D.
中科院分区：
文献类型：
--
作者：
Lin, Binzhou;Liu, Hao;Karki, Ishwor;Vik, Erik C.;Smith, Mark D.;Pellechia, Perry J.;Shimizu, Ken D.
用分子转子测量了稳定氮氧键的相互作用。通过EXSY NMR测量，分子内C=O⋅⋅N相互作用在键旋转过渡态形成，降低了旋转势垒，提高了旋转速率。烟原相互作用能与氮的正静电势有很强的相关性，这与强静电成分是一致的。相比之下，NBO扰动和锥体化分析显示没有相关性，表明轨道-轨道分量很小。当使用相同的en -苯胺转子系统测量时，最强的C=O⋅⋅N pnictogen相互作用与C=O⋅⋅C=O相互作用相当，强于C=O⋅⋅Ph相互作用。氮-烟原相互作用稳定过渡态和增强动力学过程的能力证明了它们在催化和反应设计中的潜力。
Stabilizing nitrogen pnictogen bond interactions were measured using molecular rotors. Intramolecular C=O⋅⋅⋅N interactions were formed in the bond rotation transition states which lowered the rotational barriers and increased the rates of rotation, as measured by EXSY NMR. The pnictogen interaction energies show a very strong correlation with the positive electrostatic potential on nitrogen, which was consistent with a strong electrostatic component. In contrast, the NBO perturbation and pyramidalization analyses show no correlation, suggesting that the orbital‐orbital component is minor. The strongest C=O⋅⋅⋅N pnictogen interactions were comparable to C=O⋅⋅⋅C=O interactions and were stronger than C=O⋅⋅⋅Ph interactions, when measured using the sameN‐phenylimide rotor system. The ability of the nitrogen pnictogen interactions to stabilize transition states and enhance kinetic processes demonstrates their potential in catalysis and reaction design.