Citation: Yang Zhice, Tian Jianan, Cai Hongxue, Li Li, Pan Qingjiang. Theoretical Probe for Tris(aryloxide)arene Complexed Low-valent Actinide Ions and Their Structural/Redox Properties[J]. Acta Chimica Sinica, ;2020, 78(10): 1096-1101. doi: 10.6023/A20070284 shu

Theoretical Probe for Tris(aryloxide)arene Complexed Low-valent Actinide Ions and Their Structural/Redox Properties

Key Laboratory of Functional Inorganic Material Chemistry of Education Ministry, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, China

Corresponding author: Pan Qingjiang, panqjitc@163.com
Received Date: 2 July 2020
Available Online: 3 August 2020
Fund Project: The Natural Science Foundation of Heilongjiang Province LH2019B029Project supported by the National Natural Science Foundation of China (No. 21671060), the Natural Science Foundation of Heilongjiang Province (No. LH2019B029) and the Heilongjiang Touyan Innovation Team ProgramThe National Natural Science Foundation of China 21671060

Figures(5)

It is of great significance to identify new oxidation state of actinide, which will enrich actinide coordination chemistry and advance its exploration of chemical bond and reactivity. So far, uranium with +3~+6 oxidation states has been widely recognized in complexes. Comparatively, isolated, crystallographically identified U(Ⅱ) complexes remain rare. Inspired by the pioneering work of Evans and co-workers that Y·[U^Ⅱ(Cp')₃] (Y=[K(2.2.2-cryptand)]⁺, Cp'=[C₅H₄SiMe₃]^-) was structurally characterized, several uranium(Ⅱ) complexes such as Y·[UL^E] (L^E=[(^{Ad, Me}ArO)₃ mesitylene]^3-, Ad=adamantyl), [U(NHAr^iPr6)₂] (Ar^iPr6=2, 6-(2, 4, 6-ⁱPr₃C₆H₂)₂C₆H₃), Y·[U{N(SiMe₃)₂}₃] and[U(η⁵-C₅ⁱPr₅)₂] were synthetically accessible. Inspection finds that all these U(Ⅱ) complexes were prepared in the same route, i.e., utilizing potassium graphite or potassium sphere to reduce respective U(Ⅲ) parent at low temperature. Cyclopentadiene (Cp) and arene (Ar)-based ligands are involved. They are key to determine U(Ⅱ) electron configuration, leading to 5f³6d¹ and 5f⁴, respectively. Moreover, δ(U-Ar) bonds play a significant role in stabilizing arene-ligated complexes. With the supporting of Cp-derived ligands, actinide(Ⅱ) complexes were extended to Th, Np and Pu. Unfortunately, it is not the case for the arene ligands, even with massive efforts. Given the prevailing route that actinide(Ⅱ) complex was synthesized by reducing its trivalent parent, the exploration of redox property will help to guide the synthesis of more novel U(Ⅱ) and even other actinide(Ⅱ) complexes. In this respect, theoretical computation based on accurate methodology is greatly appealing. Herein, relativistic density functional theory was exploited to investigate structural and redox properties of[AnL]^z (An=Ac~Pu; L=[(^{Me, Me}ArOH)₃Ar]^3-; z=0 and -1), where analogues of uranium complexes were experimentally known. It is found that the central arene moiety is redox-active for Ac and Th complexes in the reduction reaction, while the metal center is reduced for other complexes. So Ac and Th in reduced products still remain +3 oxidation states, whereas metals in others turn +2. The 5fⁿ electronic configuration is unraveled for actinide of[AnL]^- (An=Pa~Pu), having 3~6 electrons, respectively. Calculated redox potential (E⁰) increases from Ac to Pu in general, where U and Np show lower values than adjacent elements. A good correlation has been built between E⁰ and Δ(An-C_Ar/An-Ar_cent)/electron affinity. In brief, the study is expected to provide theoretical support for the synthesis of novel arene-based actinide(Ⅱ) complexes.
- δ(An-Ar)-type low-valent actinide complexes,
- tris(aryloxide)arene,
- electronic structure,
- redox reaction,
- relativistic density functional theory
1. [1]
  Wang, X.; Liu, Y., Nuclear Chemistry and Radiochemistry, Beijing University Press, 2007 (in Chinese).
2. [2]
  Schaedle, D.; Anwander, R. Chem. Soc. Rev. 2019, 48, 5752. doi: 10.1039/C8CS00932E
3. [3]
  Wang, D.; van Gunsteren, W. F.; Chai, Z. Chem. Soc. Rev. 2012, 41, 5836. doi: 10.1039/c2cs15354h
4. [4]
  Shi, W.-Q.; Yuan, L.-Y.; Wang, C.-Z.; Wang, L.; Mei, L.; Xiao, C.-L.; Zhang, L.; Li, Z.-J.; Zhao, Y.-L.; Chai, Z.-F. Adv. Mater. 2014, 26, 7807. doi: 10.1002/adma.201304323
5. [5]
  Wang, N.; Pang, H.; Yu, S.; Gu, P.; Song, S.; Wang, H.; Wang, X. Acta Chim. Sinica 2019, 77, 143 (in Chinese).
6. [6]
  Yue, G.; Gao, R.; Zhao, P.; Chu, M.; Shuai, M. Acta Chim. Sinica 2016, 74, 657 (in Chinese).
7. [7]
  MacDonald, M. R.; Fieser, M. E.; Bates, J. E.; Ziller, J. W.; Furche, F.; Evans, W. J. J. Am. Chem. Soc. 2013, 135, 13310. doi: 10.1021/ja406791t
8. [8]
  La Pierre, H. S.; Scheurer, A.; Heinemann, F. W.; Hieringer, W.; Meyer, K. Angew. Chem. Int. Ed. 2014, 53, 7158. doi: 10.1002/anie.201402050
9. [9]
  Billow, B. S.; Livesay, B. N.; Mokhtarzadeh, C. C.; McCracken, J.; Shores, M. P.; Boncella, J. M.; Odom, A. L. J. Am. Chem. Soc. 2018, 140, 17369. doi: 10.1021/jacs.8b10888
10. [10]
  Ryan, A. J.; Angadol, M. A.; Ziller, J. W.; Evans, W. J. Chem. Commun. 2019, 55, 2325. doi: 10.1039/C8CC08767A
11. [11]
  Guo, F.-S.; Tsoureas, N.; Huang, G.-Z.; Tong, M.-L.; Mansikkamaeki, A.; Layfield, R. A. Angew. Chem. Int. Ed. 2020, 59, 2299. doi: 10.1002/anie.201912663
12. [12]
  Windorff, C. J.; MacDonald, M. R.; Meihaus, K. R.; Ziller, J. W.; Long, J. R.; Evans, W. J. Chem. Eur. J. 2016, 22, 772. doi: 10.1002/chem.201503583
13. [13]
  Moehring, S. A.; Evans, W. J. Chem. Eur. J. 2020, 26, 1530. doi: 10.1002/chem.201905581
14. [14]
  Huh, D. N.; Ziller, J. W.; Evans, W. J. Inorg. Chem. 2018, 57, 11809. doi: 10.1021/acs.inorgchem.8b01966
15. [15]
  Langeslay, R. R.; Fieser, M. E.; Ziller, J. W.; Furche, F.; Evans, W. J. Chem. Sci. 2015, 6, 517. doi: 10.1039/C4SC03033H
16. [16]
  Su, J.; Windorff, C. J.; Batista, E. R.; Evans, W. J.; Gaunt, A. J.; Janicke, M. T.; Kozimor, S. A.; Scott, B. L.; Woen, D. H.; Yang, P. J. Am. Chem. Soc. 2018, 140, 7425. doi: 10.1021/jacs.8b03907
17. [17]
  Dutkiewicz, M. S.; Apostolidis, C.; Walter, O.; Arnold, P. L. Chem. Sci. 2017, 8, 2553. doi: 10.1039/C7SC00034K
18. [18]
  Windorff, C. J.; Chen, G. P.; Cross, J. N.; Evans, W. J.; Furche, F.; Gaunt, A. J.; Janicke, M. T.; Kozimor, S. A.; Scott, B. L. J. Am. Chem. Soc. 2017, 139, 3970. doi: 10.1021/jacs.7b00706
19. [19]
  Wu, Q. Y.; Lan, J. H.; Wang, C. Z.; Cheng, Z. P.; Chai, Z. F.; Gibson, J. K.; Shi, W. Q. Dalton Trans. 2016, 45, 3102. doi: 10.1039/C5DT04540A
20. [20]
  Chen, F.; Qu, N.; Wu, Q.; Zhang, H.; Shi, W.; Pan, Q. Acta Chim. Sinica 2017, 75, 457 (in Chinese).
21. [21]
  Zhao, S.; Zhong, Y.; Guo, Y.; Zhang, H.; Pan, Q. Acta Chim. Sinica 2016, 74, 683 (in Chinese).
22. [22]
  Zhang, X.; Wang, Y.; Morales-Martinez, R.; Zhong, J.; de Graaf, C.; Rodriguez-Fortea, A.; Poblet, J. M.; Echegoyen, L.; Feng, L.; Chen, N. J. Am. Chem. Soc. 2018, 140, 3907. doi: 10.1021/jacs.7b10865
23. [23]
  Ding, W.; Liu, Y.; Wang, D. Chem. Eur. J. 2018, 24, 19289. doi: 10.1002/chem.201804072
24. [24]
  Hu, H.-S.; Wei, F.; Wang, X.; Andrews, L.; Li, J. J. Am. Chem. Soc. 2014, 136, 1427. doi: 10.1021/ja409527u
25. [25]
  Wang, Y.-L.; Hu, H.-S.; Li, W.-L.; Wei, F.; Li, J. J. Am. Chem. Soc. 2016, 138, 1126. doi: 10.1021/jacs.5b11793
26. [26]
  Pyykko, P. J. Phys. Chem. A 2015, 119, 2326. doi: 10.1021/jp5065819
27. [27]
  Fieser, M. E.; Palumbo, C. T.; La Pierre, H. S.; Halter, D. P.; Voora, V. K.; Ziller, J. W.; Furche, F.; Meyer, K.; Evans, W. J. Chem. Sci. 2017, 8, 7424. doi: 10.1039/C7SC02337E
28. [28]
  Lewis, A. J.; Carroll, P. J.; Schelter, E. J. J. Am. Chem. Soc. 2013, 135, 13185. doi: 10.1021/ja406610r
29. [29]
  Elkechai, A.; Mani, Y.; Boucekkine, A.; Ephritikhine, M. Inorg. Chem. 2012, 51, 6943. doi: 10.1021/ic300811m
30. [30]
  Laikov, D. N.; Ustynyuk, Y. A. Russ. Chem. Bull. 2005, 54, 820. doi: 10.1007/s11172-005-0329-x
31. [31]
  Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865. doi: 10.1103/PhysRevLett.77.3865
32. [32]
  Laikov, D. N. Chem. Phys. Lett. 2005, 416, 116. doi: 10.1016/j.cplett.2005.09.046
33. [33]
  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.; Gö tz, 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., ADF (2014.06 version), SCM, Theoretical Chemistry, Vrije Universiteit, Amsterdam, The Netherlands, 2014.
34. [34]
  Klamt, A.; Schuurmann, G. J. Chem. Soc., Perkin Trans. 1993, 799.
1. [1]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
2. [2]
  Zhenming Xu , Mingbo Zheng , Zhenhui Liu , Duo Chen , Qingsheng Liu . Experimental Design of Project-Driven Teaching in Computational Materials Science: First-Principles Calculations of the LiFePO₄ Cathode Material for Lithium-Ion Batteries. University Chemistry, 2024, 39(4): 140-148. doi: 10.3866/PKU.DXHX202307022
3. [3]
  Zhaoyang WANG , Chun YANG , Yaoyao Song , Na HAN , Xiaomeng LIU , Qinglun WANG . Lanthanide(Ⅲ) complexes derived from 4′-(2-pyridyl)-2, 2′∶6′, 2″-terpyridine: Crystal structures, fluorescent and magnetic properties. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1442-1451. doi: 10.11862/CJIC.20240114
4. [4]
  Meifeng Zhu , Jin Cheng , Kai Huang , Cheng Lian , Shouhong Xu , Honglai Liu . Classical Density Functional Theory for Understanding Electrochemical Interface. University Chemistry, 2025, 40(3): 148-152. doi: 10.12461/PKU.DXHX202405166
5. [5]
  Shenhao QIU , Qingquan XIAO , Huazhu TANG , Quan XIE . First-principles study on electronic structure, optical and magnetic properties of rare earth elements X (X=Sc, Y, La, Ce, Eu) doped with two-dimensional GaSe. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2250-2258. doi: 10.11862/CJIC.20240104
6. [6]
  Xiao SANG , Qi LIU , Jianping LANG . Synthesis, structure, and fluorescence properties of Zn(Ⅱ) coordination polymers containing tetra-alkenylpyridine ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2124-2132. doi: 10.11862/CJIC.20240158
7. [7]
  Xiaoling LUO , Pintian ZOU , Xiaoyan WANG , Zheng LIU , Xiangfei KONG , Qun TANG , Sheng WANG . Synthesis, crystal structures, and properties of lanthanide metal-organic frameworks based on 2, 5-dibromoterephthalic acid ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1143-1150. doi: 10.11862/CJIC.20230271
8. [8]
  Tianyun Chen , Ruilin Xiao , Xinsheng Gu , Yunyi Shao , Qiujun Lu . Synthesis, Crystal Structure, and Mechanoluminescence Properties of Lanthanide-Based Organometallic Complexes. University Chemistry, 2024, 39(5): 363-370. doi: 10.3866/PKU.DXHX202312017
9. [9]
  Qilu DU , Li ZHAO , Peng NIE , Bo XU . Synthesis and characterization of osmium-germyl complexes stabilized by triphenyl ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1088-1094. doi: 10.11862/CJIC.20240006
10. [10]
  Changqing MIAO , Fengjiao CHEN , Wenyu LI , Shujie WEI , Yuqing YAO , Keyi WANG , Ni WANG , Xiaoyan XIN , Ming FANG . Crystal structures, DNA action, and antibacterial activities of three tetranuclear lanthanide-based complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2455-2465. doi: 10.11862/CJIC.20240192
11. [11]
  Xin MA , Ya SUN , Na SUN , Qian KANG , Jiajia ZHANG , Ruitao ZHU , Xiaoli GAO . A Tb₂ complex based on polydentate Schiff base: Crystal structure, fluorescence properties, and biological activity. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1347-1356. doi: 10.11862/CJIC.20230357
12. [12]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
13. [13]
  Jianyu Qin , Yuejiao An , Yanfeng Zhang . In Situ Assembled ZnWO₄/g-C₃N₄ S-Scheme Heterojunction with Nitrogen Defect for CO₂ Photoreduction. Acta Physico-Chimica Sinica, 2024, 40(12): 2408002-. doi: 10.3866/PKU.WHXB202408002
14. [14]
  Yanan Liu , Yufei He , Dianqing Li . Preparation of Highly Dispersed LDHs-based Catalysts and Testing of Nitro Compound Reduction Performance: A Comprehensive Chemical Experiment for Research Transformation. University Chemistry, 2024, 39(8): 306-313. doi: 10.3866/PKU.DXHX202401081
15. [15]
  Liyang ZHANG , Dongdong YANG , Ning LI , Yuanyu YANG , Qi MA . Crystal structures, luminescent properties and Hirshfeld surface analyses of three cadmium(Ⅱ) complexes based on 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1943-1952. doi: 10.11862/CJIC.20240079
16. [16]
  Jingwen Wang , Minghao Wu , Xing Zuo , Yaofeng Yuan , Yahao Wang , Xiaoshun Zhou , Jianfeng Yan . Advances in the Application of Electrochemical Regulation in Investigating the Electron Transport Properties of Single-Molecule Junctions. University Chemistry, 2025, 40(3): 291-301. doi: 10.12461/PKU.DXHX202406023
17. [17]
  Xiaofeng Zhu , Bingbing Xiao , Jiaxin Su , Shuai Wang , Qingran Zhang , Jun Wang . Transition Metal Oxides/Chalcogenides for Electrochemical Oxygen Reduction into Hydrogen Peroxides. Acta Physico-Chimica Sinica, 2024, 40(12): 2407005-. doi: 10.3866/PKU.WHXB202407005
18. [18]
  Zitong Chen , Zipei Su , Jiangfeng Qian . Aromatic Alkali Metal Reagents: Structures, Properties and Applications. University Chemistry, 2024, 39(8): 149-162. doi: 10.3866/PKU.DXHX202311054
19. [19]
  Haitang WANG , Yanni LING , Xiaqing MA , Yuxin CHEN , Rui ZHANG , Keyi WANG , Ying ZHANG , Wenmin WANG . Construction, crystal structures, and biological activities of two Ln^Ⅲ₃ complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1474-1482. doi: 10.11862/CJIC.20240188
20. [20]
  Ji Qi , Jianan Zhu , Yanxu Zhang , Jiahao Yang , Chunting Zhang . Visible Color Change of Copper (II) Complexes in Reversible SCSC Transformation: The Effect of Structure on Color. University Chemistry, 2024, 39(3): 43-57. doi: 10.3866/PKU.DXHX202307050

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(731)
HTML views(67)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142