二价双核铀聚吡咯配合物结构设计和铀-铀多重键的理论研究

doi:10.6023/A17010008

化学学报 ›› 2017, Vol. 75 ›› Issue (5): 457-463.DOI: 10.6023/A17010008 上一篇下一篇

研究论文

二价双核铀聚吡咯配合物结构设计和铀-铀多重键的理论研究

陈方园^a, 曲宁^a, 吴群燕^b, 张红星^c, 石伟群^b, 潘清江^a

a. 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;
b. 中国科学院高能物理研究所核能放射化学实验室北京 100049;
c. 吉林大学理论化学研究所长春 130023

投稿日期:2017-01-09 发布日期:2017-04-01
通讯作者: 潘清江, 石伟群 E-mail:panqjitc@163.com;shiwq@ihep.ac.cn
基金资助:
项目由国家自然科学基金（Nos.21273063，21477130）和黑龙江省留学回国人员科技项目择优资助.

Structures and Uranium-Uranium Multiple Bond of Binuclear Divalent Uranium Complex of Pyrrolic Schiff-base Macrocycle: a Relativistic DFT Probe

Chen Fangyuan^a, Qu Ning^a, Wu Qunyan^b, Zhang Hongxing^c, Shi Weiqun^b, Pan Qingjiang^a

a. Key Laboratory of Functional Inorganic Material Chemistry of Education Ministry, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080;
b. Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China;
c. Institute of Theoretical Chemistry, Jilin University, Changchun 130023

Received:2017-01-09 Published:2017-04-01
Contact: 10.6023/A17010008 E-mail:panqjitc@163.com;shiwq@ihep.ac.cn
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. 21273063, 21477130) and the Scientific Foundation of Heilongjiang Province for the Returned Overseas Chinese Scholars.

文章分享

1. 二价双核铀聚吡咯配合物结构设计和铀-铀多重键的理论研究.PDF(1313KB)

摘要/Abstract

经三十余年努力，二价铀溶液化学于近年取得突破性进展，Evans和Meyer等成功获得两个可通过X-ray晶体衍射表征结构的有机金属铀（II）配合物.为进一步拓展U^II配合物化学和探索可能存在的金属多重键，设计双核配合物[（U^II）₂（L）]（L为八齿氮供体低聚吡咯大环四价阴离子），并使用相对论密度泛函理论优化其可能的电子自旋态异构体结构和计算相关性质.结果表明，[（U^II）₂（L）]具有三重态基态，其电子组态为π⁴σ²δ²；U（5f）原子轨道对高占据分子轨道有重要贡献；它的U—U键长为2.33Å、Mayer键级为3.89和对应的伸缩振动频率为259 cm^-1，被指认为U—U弱四重键.这一结论与QTAIM （quantum theory of atoms in molecule）的U—U键临界点处的电子/能量密度拓扑分析结果相一致.与不同氧化态铀同类物[（U^m）₂（L）]ⁿ⁺ （m=III，n=2；m=IV，n=4）比较显示，随着铀氧化态增大，U—U距离增长、键级变小、伸缩振动频率变小，金属铀电子自旋密度与常规预期值的差值（?S_U）增大；结合分子轨道和QTAIM参数分析，发现金属氧化态可以调控配体和金属轨道能级匹配程度和改变金属-金属多重键.

关键词: 双核U^II聚吡咯配合物, 电子结构, 铀-铀多重键, QTAIM拓扑分析, 相对论密度泛函理论

Although attempts to synthesize divalent uranium molecules were begun three decades ago, molecular U(II) species isolable in solution have been not achieved until recent years. In 2013, Evans and co-workers synthesized the first U(II) complex, [U(Cp')₃]·[K(2,2,2-cryptand)] (Cp'=C₅H₄SiMe₃) via flash reduction, that was suitable for X-ray crystal diffraction characterization. A year later, the group of Meyer obtained another divalent uranium complex, [U((^Ad,MeArO)₃mes)]·[K(2,2,2-cryptand)] employing their particularly interesting tris(aryloxide) arene ligand. The 5f³6d¹ and 5f⁴ ground states were assigned to these two complexes, respectively, by the jointed experimental/theoretical studies. It was demonstrated that the ligand significantly affect the nature of the ground state of divalent uranium complex by tuning the energetic separation of the 5f and 6d orbitals. Therefore, careful selection of ligand makes it possible to have access to +II oxidation state of uranium and prepare new U^II complex. A flexible octadentate polypyrrollic Schiff-base macrocycle (H₄L) has been developed to complex a variety of metals such as actinides, rare earth and transition metals that show a wide range of size and diverse oxidation states. Both mono- and bimetallic complexes featured with an intriguing “Pacman-like” structure were obtained. For example, the reaction of H₄L with a trivalent uranium precursor [(U^III)I₃(THF)₄] yielded a neutral [(U^IV)(L)] complex, where the uranium ion was determined by the single crystal X-ray diffraction to be situated inside the ligand mouth and held by eight nitrogen atoms together. The +IV oxidation state was assigned to the uranium by presuming dihydrogen elimination. Considering the flexibility, tetravalent-anion nature as well as capability of accommodating bimetallic ions and stabilizing various oxidation states of uranium (e.g. III~VI complexes have been found so far) that the polypyrrolic ligand has exhibited in previously synthesized complexes, two divalent uranium ions would be likely complexated by the ligand to generate a complex, [(U^II)₂(L)]. In addition to enriching the coordination chemistry of U(II), it is also a good example to explore electronic structures of the low-valent uranium complex and unravel the uranium-uranium multiple bonding nature. Although many theoretical studies have explored uranium complexes, the study focusing on the divalent diuranium complex of a single macrocyclic ligand remains rare. In the work, a relativistic density functional theory has been employed to investigate [(U^II)₂(L)]. The structures in electron spin states (singlet, triplet, quintet, septet and nonet) were optimized. Short distances of U—U (2.32~2.67 Å), large bond order (2.95~3.90) and high stretching vibrational frequencies (180~263 cm^-1) were calculated. Energetic calculations find that its triplet state is the ground state. It has the electronic configuration of π⁴σ²δ², primarily contributed by U(5f) character. Structural and molecular-orbital analyses suggest a slightly weak uranium-uranium quadruple bond, which is confirmed by the quantum theory of atoms in molecule (QTAIM) calculations. Further comparison with analogues [(U^III)₂(L)]²⁺ and [(U^IV)₂(L)]⁴⁺ was also addressed. It is found that the uranium oxidation state is able to tune the energetic matching between the highest-energy occupied orbital of ligand and the adjacent low-energy metal-based orbital, as well as correlates with the electron transfer between metal and ligand and the diuranium multiple bond number.

Key words: bimetallic U^II polypyrrolic complexes, electronic structures, diuranium multiple bond, QTAIM, relativistic DFT

引用此文

陈方园, 曲宁, 吴群燕, 张红星, 石伟群, 潘清江. 二价双核铀聚吡咯配合物结构设计和铀-铀多重键的理论研究[J]. 化学学报, 2017, 75(5): 457-463.

Chen Fangyuan, Qu Ning, Wu Qunyan, Zhang Hongxing, Shi Weiqun, Pan Qingjiang. Structures and Uranium-Uranium Multiple Bond of Binuclear Divalent Uranium Complex of Pyrrolic Schiff-base Macrocycle: a Relativistic DFT Probe[J]. Acta Chim. Sinica, 2017, 75(5): 457-463.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] Hashke, J. M.; Stakebake, J. L. In The Chemistry of the Actinide and Transactinide Elements, Eds.: Morss, L. R.; Edelstein, N. M.; Fuger, J., Springer, Netherlands, 2006, p. 3199.
[2] Liddle, S. T. Angew. Chem. Int. Ed. 2015, 54, 8604.
[3] MacDonald, M. R.; Fieser, M. E.; Bates, J. E.; Ziller, J. W.; Furche, F.; Evans, W. J. J. Am. Chem. Soc. 2013, 135, 13310.
[4] La Pierre, H. S.; Scheurer, A.; Heinemann, F. W.; Hieringer, W.; Meyer, K. Angew. Chem. Int. Ed. 2014, 53, 7158.
[5] Meyer, G. Angew. Chem. Int. Ed. 2014, 53, 3550.
[6] Sessler, J. L.; Cho, W. S.; Dudek, S. P.; Hicks, L.; Lynch, V. M.; Huggins, M. T. J. Porphyr. Phthalocyanines 2003, 7, 97.
[7] Givaja, G.; Blake, A. J.; Wilson, C.; Schroder, M.; Love, J. B. Chem. Commun. 2003, 2508.
[8] Arnold, P. L.; Patel, D.; Wilson, C.; Love, J. B. Nature 2008, 451, 315.
[9] Arnold, P. L.; Potter, N. A.; Magnani, N.; Apostolidis, C.; Griveau, J.-C.; Colineau, E.; Morgenstern, A.; Caciuffo, R.; Love, J. B. Inorg. Chem. 2010, 49, 5341.
[10] Arnold, P. L.; Potter, N. A.; Carmichael, C. D.; Slawin, A. M. Z.; Roussel, P.; Love, J. B. Chem. Commun. 2010, 46, 1833.
[11] Arnold, P. L.; Hollis, E.; White, F. J.; Magnani, N.; Caciuffo, R.; Love, J. B. Angew. Chem. Int. Ed. 2011, 50, 887.
[12] Arnold, P. L.; Jones, G. M.; Odoh, S. O.; Schreckenbach, G.; Magnani, N.; Love, J. B. Nat. Chem. 2012, 4, 221.
[13] Zegke, M.; Nichol, G. S.; Arnold, P. L.; Love, J. B. Chem. Commun. 2015, 51, 5876.
[14] Su, D.-M.; Zheng, X.-J.; Schreckenbach, G.; Pan, Q.-J. Organometallics 2015, 34, 5225.
[15] Laikov, D. N.; Ustynyuk, Y. A. Russ. Chem. Bull. 2005, 54, 820.
[16] Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865.
[17] Baerends, E. J.; Ziegler, T.; Autschbach, J.; Bashford, D.; Bérces, A.; Bickelhaupt, F. M.; Bo, C.; Boerrigter, P. M.; Cavallo, L.; Chong, D. P.; Deng, L.; Dickson, R. M.; Ellis, D. E.; van Faassen, M.; Fan, L.; Fischer, T. H.; Fonseca Guerra, C.; Franchini, M.; Ghysels, A.; Giammona, A.; van Gisbergen, S. J. A.; Götz, A. W.; Groeneveld, J. A.; Gritsenko, O. V.; Grüning, M.; Gusarov, S.; Harris, F. E.; van den Hoek, P.; Jacob, C. R.; Jacobsen, H.; Jensen, L.; Kaminski, J. W.; van Kesse, G.; Kootstra, F.; Kovalenko, A.; Krykunov, M. V.; van Lenthe, E.; McCormack, D. A.; Michalak, A.; Mitoraj, M.; Morton, S. M.; Neugebauer, J.; Nicu, V. P.; Noodleman, L.; Osinga, V. P.; Patchkovskii, S.; Pavanello, M.; Philipsen, P. H. T.; Post, D.; Pye, C. C.; Ravenek, W.; Rodríguez, J. I.; Ros, P.; Schipper, P. R. T.; van Schoot, H.; Schreckenbach, G.; Seldenthuis, J. S.; Seth, M.; Snijders, J. G.; Solà, M.; Swart, M.; Swerhone, D.; te Velde, G.; Vernooijs, P.; Versluis, L.; Visscher, L.; Visser, O.; Wang, F.; Wesolowski, T. A.; van Wezenbeek, E. M.; Wiesenekker, G.; Wolff, S. K.; Woo, T. K.; Yakovlev, A. L.; ADF2014.06 ed.; SCM, Theoretical Chemistry, Vrije Universiteit: Amsterdam, The Netherlands, 2014.
[18] Klamt, A.; Jonas, V.; Burger, T.; Lohrenz, J. C. W. J. Phys. Chem. A 1998, 102, 5074.
[19] Bao, Z.; Zhao, H.-B.; Qu, N.; Schreckenbach, G.; Pan, Q.-J. Dalton Trans. 2016, 45, 15970.
[20] Zhao, S.; Zhong, Y.; Guo, Y.; Zhang, H.; Pan, Q. Acta Chim. Sinica 2016, 74, 683. (赵思魏, 钟宇曦, 郭元茹, 张红星, 潘清江, 化学学报, 2016, 74, 683.)
[21] van Lenthe, E.; Baerends, E. J.; Snijders, J. G. J. Chem. Phys. 1993, 99, 4597.
[22] Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R. P., C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J.; Gaussian 09, Revision D.01 ed. Gaussian, Inc., Wallingford CT, 2009.
[23] Cao, X.; Dolg, M.; Stoll, H. J. Chem. Phys. 2003, 118, 487.
[24] Lu, T.; Chen, F. J. Comput. Chem. 2012, 33, 580.
[25] Patel, D.; Liddle, S. T. Rev. Inorg. Chem. 2012, 32, 1.
[26] Patel, D.; King, D. M.; Gardner, B. M.; McMaster, J.; Lewis, W.; Blake, A. J.; Liddle, S. T. Chem. Commun. 2011, 47, 295.
[27] Gardner, B. M.; Patel, D.; Cornish, A. D.; McMaster, J.; Lewis, W.; Blake, A. J.; Liddle, S. T. Chem. Eur. J. 2011, 17, 11266.
[28] Liddle, S. T.; McMaster, J.; Mills, D. P.; Blake, A. J.; Jones, C.; Woodul, W. D. Angew. Chem. Int. Ed. 2009, 48, 1077.
[29] Hlina, J. A.; Pankhurst, J. R.; Kaltsoyannis, N.; Arnold, P. L. J. Am. Chem. Soc. 2016, 138, 3333.
[30] Cavigliasso, G.; Kaltsoyannis, N. Inorg. Chem. 2006, 45, 6828.
[31] Cavigliasso, G.; Kaltsoyannis, N. Dalton Trans. 2006, 5476.
[32] Roos, B. O.; Gagliardi, L. Inorg. Chem. 2006, 45, 803.
[33] Zhou, J.; Sonnenberg, J. L.; Schlegel, H. B. Inorg. Chem. 2010, 49, 6545.
[34] Long, B.; Bao, J. L.; Truhlar, D. G. J. Am. Chem. Soc. 2016, 138, 14409.
[35] Xiong, Z.; Chen, Q.; Zheng, X.; Wei, X. Acta Chim. Sinica 2005, 63, 572. (熊忠华, 陈琦, 郑秀梅, 魏锡文, 化学学报, 2005, 63, 572.)
[36] Zhang, Y.; Ma, X.; Zhang, X.; Lei, M. Acta Chim. Sinica 2016, 74, 340. (张益伟, 马雪璐, 张欣, 雷鸣, 化学学报, 2016, 74, 340.)
[37] Yang, Y.; Zhang, Q.; Shi, J.; Fu, Y. Acta Chim. Sinica 2016, 74, 422. (杨一诺, 张琪, 石景, 傅尧, 化学学报, 2016, 74, 422.)
[38] Kirker, I.; Kaltsoyannis, N. Dalton Trans. 2011, 40, 124.
[39] Tassell, M. J.; Kaltsoyannis, N. Dalton Trans. 2010, 39, 6719.
[40] Liu, J.-B.; Chen, G. P.; Huang, W.; Clark, D. L.; Schwarz, W. H. E.; Li, J. Dalton Trans. 2017, 46, 2542.

二价双核铀聚吡咯配合物结构设计和铀-铀多重键的理论研究

Structures and Uranium-Uranium Multiple Bond of Binuclear Divalent Uranium Complex of Pyrrolic Schiff-base Macrocycle: a Relativistic DFT Probe

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

参考文献

相关文章 15

编辑推荐

相关统计

本文评价

[1]	张凯, 武晓君. 具有室温铁磁性的二维Janus钛硫属化物^★[J]. 化学学报, 2023, 81(9): 1142-1147.
[2]	梁雪峰, 荆剑, 冯昕, 赵勇泽, 唐新员, 何燕, 张立胜, 李慧芳. 共价有机框架COF66/COF366的电子结构: 从单体到二维平面聚合物[J]. 化学学报, 2023, 81(7): 717-724.
[3]	赵政嘉, 刘康, 郭燕, 于吉攀, 石伟群. 超铀金属有机化学研究进展[J]. 化学学报, 2023, 81(11): 1633-1641.
[4]	郑冰, 王喆, 何静, 张姣, 戚文博, 张梦圆, 于海涛. 碱(土)金属/双层α-硼烯纳米复合体的结构和功函性质的理论研究[J]. 化学学报, 2023, 81(10): 1357-1370.
[5]	龚雪, 马新国, 万锋达, 段汪洋, 杨小玲, 朱进容. 二维单层MoSi₂X₄ (X=N, P, As)的电子结构及光学性质研究[J]. 化学学报, 2022, 80(4): 510-516.
[6]	刘康, 李斌, 于吉攀, 石伟群. 十四族卡本衍生物: 一类重要的活性中间体[J]. 化学学报, 2022, 80(3): 373-385.
[7]	邓颖怡, 钱银银, 谢颖, 张磊, 郑冰, 娄原青, 于海涛. Li吸附对双层α-硼烯功函调控作用的理论研究[J]. 化学学报, 2020, 78(4): 344-354.
[8]	杨之策, 田佳楠, 才洪雪, 李丽, 潘清江. 三(芳氧基)芳烃络合低价锕系离子的结构和还原性质理论探索[J]. 化学学报, 2020, 78(10): 1096-1101.
[9]	李磊, 贾桂霄, 王晓霞, 吴铜伟, 宋希文, 安胜利. 基于缺陷曲率对含有V₁~V₄空位(5,5)单壁碳纳米管[1+1]和[2+1]加成反应的第一性原理研究[J]. 化学学报, 2017, 75(3): 284-292.
[10]	赵思魏, 钟宇曦, 郭元茹, 张红星, 潘清江. 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[J]. 化学学报, 2016, 74(8): 683-688.
[11]	吴其胜, 王子路, 王金兰. 单轴应变对石墨烯掺杂硼、氮、铝、硅、磷的影响与调控[J]. 化学学报, 2014, 72(12): 1233-1237.
[12]	孙小丽, 李吉来, 黄旭日, 孙家锺. Fe⁺与CH₃X (X=Cl, Br, I)反应的理论研究[J]. 化学学报, 2013, 71(05): 749-754.
[13]	黄晓, 谭莹, 许旋, 徐志广. 电场对杂金属串配合物[CuCuM(npa)₄Cl]⁺(M=Pt, Pd, Ni)结构影响的理论研究[J]. 化学学报, 2012, 70(18): 1979-1986.
[14]	仇毅翔, 王曙光. 三(五甲基环戊二烯基)稀土金属配合物(C₅Me₅)₃Ln (Ln=Sc, Y, La)的量子化学理论研究[J]. 化学学报, 2012, 70(18): 1930-1938.
[15]	王剑锋, 贾建峰, 马丽娟, 武海顺. TiB_n (n＝1～12)团簇的结构与稳定性: 基于从头算的研究[J]. 化学学报, 2012, 70(15): 1643-1649.