中文摘要：

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.

英文摘要：

Uranium complexes play an increasingly important role in the fields of power resource, environment and medical science. As the most stable and the most prevalent formation of uranium, hexavalent uranyl species（UO2^2＋） are widely present in the natural water system and the nuclear fuel cycle. Since 2005, the isoelectronic analogue of the uranyl, U（NR）2^2＋,（R=alkyl and aryl） has been a burgeoning area of research. Many bis-imido uranium complexes have been synthesized and investigated for their structural, reactivity and spectroscopic properties. It is found that the bis-imido uranium（VI） complex is capable of undergoing imido exchange reaction with oxo group, but the contrary reaction can not occur. Recently, a flexible polypyrrolic macrocycle（H4L） has been widely used to complexate hexavalent UO^2＋. An interesting Pacman-like complex, [（THF）（U^VIO2）（H2L）], was obtained, where the uranyl ion is accommodated by one N4-donor compartment and the other compartment remains vacant. In the equatorial plane of linear uranyl ion, one THF solvent serves as the fifth coordination. Notably, two hydrogen bonds are formed between the endo-oxo of uranyl and remaining hydrogen atoms of two pyrrolides in the second compartment of macrocycle. In this work, a series of uranium complexes of the polypyrrolic macrocycle with the mixed oxo and imido groups, [（THF）（OUE）（A2L）]（E=NH, NMe and NPh; A=H and Li; labeled as UE-A） were designed, on the basis of their dioxo analogues UO-A（E=O） where the UO-H was experimentally synthesized and characterized. Their structures, Infrared（IR） vibrational spectra and oxo-imido exchange reaction were examined by the scalar relativistic density functional theory（DFT）. The U=Oendo bond lengths of UE-A were optimized to be within 1.84-1.89A, longer than those of known uranyl complexes which possess regular pentagonal dipyramidal structure. This is related to the interaction between the A and endo-oxo atoms. The calculated U=N distances range