Acta Chim. Sinica ›› 2016, Vol. 74 ›› Issue (8): 683-688.

Article

聚吡咯铀酰氧-酰亚胺配合物结构、振动光谱和基团交换反应的相对论密度泛函理论计算

1. a 东北林业大学生物质材料科学与技术教育部重点实验室 材料科学与工程学院 哈尔滨 150040;
b 黑龙江大学功能无机材料化学教育部重点实验室 化学化工与材料学院 哈尔滨 150080;
c 吉林大学理论化学研究所 长春 130023
• 投稿日期:2016-06-14 发布日期:2016-08-10
• 通讯作者: 潘清江, 郭元茹 E-mail:guoyrnefu@163.com;panqjitc@163.com
• 基金资助:

项目受中央高校基本科研业务费专项资金（No. DL12EB05-02）、国家（No. 21273063）和黑龙江省（No. B201318）自然科学基金以及黑龙江省留学回国人员科技项目择优资助.

A Relativistic DFT Study of Mixed Oxo-Imido Uranium Complexes of Polypyrrolic Macrocycle: Structure, Vibrational Spectrum and Oxo/Imido Exchange Reaction

Zhao Siweia, Zhong Yuxib, Guo Yuanrua, Zhang Hongxingc, Pan Qingjiangb

1. a Key Laboratory of Bio-based Material Science & Technology of Education Ministry, College of Material Science and Engineering, Northeast Forestry University, Harbin 150040;
b Key Laboratory of Functional Inorganic Material Chemistry of Education Ministry, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080;
c Institute of Theoretical Chemistry, Jilin University, Changchun 130023
• Received:2016-06-14 Published:2016-08-10
• Supported by:

Project supported by the Fundamental Research Funds for the Central Universities (No. DL12EB05-02), the Natural Science Foundations of China (No. 21273063) and of Heilongjiang Province (No. B201318), and the Scientific Foundation of Heilongjiang Province for the Returned Overseas Chinese Scholars.

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 (UO22+) are widely present in the natural water system and the nuclear fuel cycle. Since 2005, the isoelectronic analogue of the uranyl, U(NR)22+, (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 UO2+. An interesting Pacman-like complex, [(THF)(UVIO2)(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 1.84～1.89 Å, 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 from 1.87 to 1.90 Å, which are affected by various R substituent (direct effect) and different A atom that is bonding to endo-oxo atom (indirect effect). All the calculated U=O/U=N distances fall well within the range of experimental values. The partial triple character is unraveled for U=Oexo and U=N bonds, but a modest one between single and double is assigned to U=Oendo of UE-Li. Frequency calculations find the close bonding properties for O=U=NH and O=U=O, both of which show symmetrical and asymmetrical stretching vibrational bands between 700 and 900 cm-1. The introduction of steric substituents of Me and Ph leads to two greatly separate peaks of U=O and U=N-C. The strong coupling of Me and Ph with U=N bonding makes the U=N-C vibrations present in the high-frequency region from 1166 to 1266 cm-1, which are comparable to experimental values of 1170～1270 cm-1 for U=N-R (R=tBu and Ph). The variation of the A atom from H to Li significantly redshifts the U=O and U=N-C stretches. When carefully selecting the A atom and the R substituent, the Pacman-like complex UO-A would be easier to undergo the oxo exchange with the imido group, compared with regular pentagonal dipyrimid complex. This study is expected to provide theoretical support for experimental study of mixed oxo-imido uranium complex.