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铀酰氧-酰亚胺混合型配合物的合成为热力学稳定、动力学惰性铀酰(UO22+)和等电子体系铀酰亚胺(U(NR)22+)研究建立了纽带.使用相对论密度泛函理论计算“Pacman”结构配合物[(THF)(OUVIE)(A2L)](E=O、NH、NMe和NPh;A=H和Li;L为八齿氮供体低聚吡咯大环配体).优化得到U=O/U=N距离与实验值符合;键级和电子结构分析显示U=Oexo/U=N有部分三重键特征;由于受Li离子扰动,U=Oendo强度则介于单键和双键之间.计算表明O=U=NH和O=U=O成键相近,均具有对称和反对称伸缩振动频率,而取代基Me和Ph耦合作用使得U=N—C吸收峰出现在高频区域.酰氧和酰亚胺基团交换反应计算发现独特Pacman结构配合物的反应能相对五角双锥型配合物的有所降低,其中=O与=NMe交换反应最易实现;A离子变换不但能调控配合物结构和特征振动谱,还可降低基团交换反应能.
The synthesis of uranyl-oxy-imide complexes is a bond for the study of thermodynamically stable, kinetic inert uranyl (UO22 +) and the equivalent electronic system uranimide (U (NR) 22+) Functional theory calculations “Pacman” structure complex [(THF) (OUVIE) (A2L)] (E = O, NH, NMe and NPh; A = H and Li; Ring ligand.) The optimized U = O / U = N distance agrees well with the experimental data. The bond order and electronic structure analysis show that U = Oexo / U = N has some triple bond features; U = Oendo intensity due to Li ion perturbation Between the single bond and the double bond.The calculations show that the symmetric and antisymmetric stretching vibrational frequencies of O = U = NH and O = U = O are close to each other, and the coupling effect of the substituents Me and Ph makes U = N -C absorption peak appears in the high frequency region.The calculation of the exchange reaction of acyl oxygen and imide groups shows that the reaction of the unique Pacman structure complex can be reduced relative to the pentagonal bipyramid complex with = O and = NMe exchange reaction The most easy to achieve; A ion conversion can not only regulate the structure of the complex and the characteristic vibration spectrum, but also reduce the group exchange reaction energy.