Citation: Yu-Xuan REN, Shuai-Tao WANG, Chen-Xu ZHANG, Huan-Ming WANG, Gui-Hui LI. Synthesis, Crystal Structure of Protic Pyrazolium Ionic Liquid and Its Catalytic Properties for CO₂ Cycloaddition[J]. Chinese Journal of Structural Chemistry, ;2020, 39(4): 801-808. doi: 10.14102/j.cnki.0254-5861.2011-2500 shu

Synthesis, Crystal Structure of Protic Pyrazolium Ionic Liquid and Its Catalytic Properties for CO₂ Cycloaddition

a.
Minsheng College, Henan University, Kaifeng 475004, China
b.
The Key Laboratory for Special Functional Materials, Henan University, Kaifeng 475004, China

Corresponding author: Gui-Hui LI, tzgncl@henu.edu.cn
Received Date: 17 June 2019
Accepted Date: 11 October 2019

Fund Project: the Key Scientific Research Plan Projects of Henan Province 18A150024Innovation and entrepreneurship support program for college students of Minsheng College, Henan University MSCXCY2018006

Figures(4)

Two protic pyrazolium ionic liquids (ILs) are synthesized and characterized by mass spectra (MS), ¹H NMR, ¹³C NMR, and single-crystal X-ray diffraction. Then, their catalytic activity for the cycloaddition of PO and CO₂ is investigated. Two protic pyrazolium ILs are the orthorhombic and triclinic systems of space groups Cmca and C2/c for HTMPzBr and HDMPzBr, respectively. They could catalyze the cycloaddition reaction of carbon dioxide (CO₂) with epoxides (PO) to produce cyclic carbonate (PC) without any solvent and co-catalyst and show strong catalytic activity when the reaction temperature is over 110 ℃.
- protic pyrazolium ionic liquids,
- carbon dioxide,
- epoxide,
- cyclic carbonate,
- crystal structure
1. [1]
  Barker, R.; Hua, Y.; Neville, A. Internal corrosion of carbon steel pipelines for dense-phase CO₂ transport in carbon capture and storage (CCS)–a review. Int. Mater. Rev. 2017, 62, 1–31. doi: 10.1080/09506608.2016.1176306
2. [2]
  Olah, G. A.; Prakash, G. K. S.; Goeppert, A. Anthropogenic chemical carbon cycle for a sustainable future. J. Am. Chem. Soc. 2011, 133, 12881–12898. doi: 10.1021/ja202642y
3. [3]
  Sakakura, T.; Choi, J. C.; Yasuda, H. Transformation of carbon dioxide. Chem. Rev. 2007, 107, 2365–2387. doi: 10.1021/cr068357u
4. [4]
  Yang, X. F.; Kattel, S.; Senanayake, S. D.; Boscoboinik, J. A.; Nie, X. W.; Graciani, J.; Rodriguez, J. A.; Liu, P.; Stacchiola, D. J.; Chen, J. G. Low pressure CO₂ hydrogenation to methanol over gold nanoparticles activated on a CeO_x/TiO₂ interface. J. Am. Chem. Soc. 2015, 137, 10104–10107. doi: 10.1021/jacs.5b06150
5. [5]
  Darensbourg, D. J.; Kyran, S. J. Carbon dioxide copolymerization study with a sterically encumbering naphthalene-derived oxide. ACS Catal. 2015, 5, 5421–5430. doi: 10.1021/acscatal.5b01375
6. [6]
  Xie, J. N.; Yu, B.; Guo, C. X.; He, L. N. Copper(Ⅰ)/phosphine-catalyzed tandem carboxylation/annulation of terminal alkynes under ambient pressure of CO₂: one-pot access to 3a-hydroxyisoxazolo [3, 2-a] isoindol-8 (3aH)-ones. Green Chem. 2015, 17, 4061–4067. doi: 10.1039/C5GC00926J
7. [7]
  Jiang, X.; Gou, F. L.; Fu, X. Y.; Jing, H. W. Ionic liquids-functionalized porphyrins as bifunctional catalysts for cycloaddition of carbon dioxide to epoxides. J. CO₂ Util. 2016, 16, 264–271. doi: 10.1016/j.jcou.2016.08.003
8. [8]
  Doskocil, E. J. Effect of water and alkali modifications on ETS-10 for the cycloaddition of CO₂ to propylene oxide. J. Phys. Chem. B 2005, 109, 2315–2320. doi: 10.1021/jp048870g
9. [9]
  Kihara, N.; Hara, N.; Endo, T. Catalytic activity of various salts in the reaction of 2, 3-epoxypropyl phenyl ether and carbon dioxide under atmospheric pressure. J. Org. Chem. 1993, 58, 6198–6202. doi: 10.1021/jo00075a011
10. [10]
  Huang, J. W.; Shi, M. Chemical fixation of carbon dioxide by NaI/PPh₃/PhOH. J. Org. Chem. 2003, 68, 6705–6709. doi: 10.1021/jo0348221
11. [11]
  Liang, S. G.; Liu, H. Z.; Jiang, T.; Song, J. L.; Yang, G. Y.; Han, B. X. Highly efficient synthesis of cyclic carbonates from CO₂ and epoxides over cellulose/KI. Chem. Comm. 2011, 47, 2131–2133. doi: 10.1039/C0CC04829A
12. [12]
  Wang, B. S.; Feng, X.; Zhang, L. F.; Yang, S. J.; Jiang, X. Z.; Zhou, J.; Gao, G. H. One-pot reaction of CO₂, epichlorohydrin and amine to synthesize 4-(phenylamino) methyl-ethylene carbonate catalyzed by ionic liquids. J. CO₂ Util. 2013, 1, 88–91. doi: 10.1016/j.jcou.2013.02.001
13. [13]
  Chen, F. F.; Huang, K.; Zhou, Y.; Tian, Z. Q.; Zhu, X.; Tao, D. J.; Jiang, D.; Dai, S. Multi-molar absorption of CO₂ by the activation of carboxylate groups in amino acid ionic liquids. Angew. Chem. Int. Ed. 2016, 55, 7166–7170. doi: 10.1002/anie.201602919
14. [14]
  Wang, L.; Jin, X. F.; Li, P.; Zhang, J. L.; He, H. Y.; Zhang, S. J. Hydroxyl-functionalized ionic liquid promoted CO₂ fixation according to electrostatic attraction and hydrogen bonding interaction. Ind. Eng. Chem. Res. 2014, 53, 8426–8435. doi: 10.1021/ie501063f
15. [15]
  Zheng, D. N.; Zhang, J. S.; Zhu, X. R.; Ren, T. G.; Wang, L.; Zhang, J. L. Solvent effects on the coupling reaction of CO₂ with PO catalyzed by hydroxyl imidazolium ionic liquid: comparison of different models. J. CO₂ Util. 2018, 27, 99–106. doi: 10.1016/j.jcou.2018.07.005
16. [16]
  Sun, J. M.; Fujita, S. I.; Zhao, F. Y.; Arai, M. Synthesis of styrene carbonate from styrene oxide and carbon dioxide in the presence of zinc bromide and ionic liquid under mild conditions. Green Chem. 2004, 6, 613–616. doi: 10.1039/b413229g
17. [17]
  Angell, C. A.; Ansari, Y.; Zhao, Z. Ionic liquids past, present and future. Faraday Discuss. 2012, 154, 9–27. doi: 10.1039/C1FD00112D
18. [18]
  Aoyagi, N.; Furusho, Y.; Endo, T. Convenient synthesis of cyclic carbonates from CO₂ and epoxides by simple secondary and primary ammonium iodides as metal-free catalysts under mild conditions and its application to synthesis of polymer bearing cyclic carbonate moiety. J. Polym. Sci. A Pol. Chem. 2013, 51, 1230–1242. doi: 10.1002/pola.26492
19. [19]
  Xiao, L. F.; Su, D.; Yue, C. T.; Wu, W. Protic ionic liquids: a highly efficient catalyst for synthesis of cyclic carbonate from carbon dioxide and epoxides. J. CO₂ Util. 2014, 6, 1–6. doi: 10.1016/j.jcou.2014.01.004
20. [20]
  Earle, M. J.; Seddon, K. R. Ionic liquids. Green solvents for the future. Pure Appl. Chem. 2000, 72, 1391–1398. doi: 10.1351/pac200072071391
21. [21]
  Gordon, C. M.; Holbrey, J. D.; Kennedy, A. R.; Seddon, K. R. Ionic liquid crystals: hexafluorophosphate salts. J. Mater Chem. 1998, 8, 2627–2636. doi: 10.1039/a806169f
22. [22]
  Roche, D. J.; Gordon, C. M.; Imrie, C. T.; Ingram, M. D.; Kennedy, A. R.; Celso, L. F.; Triolo, A. Application of complementary experimental techniques to characterization of the phase behavior of [C16mim][PF6] and [C14mim][PF6]. Chem. Mater. 2003, 15, 3089–3097. doi: 10.1021/cm021378u
23. [23]
  Abdallah, D. J.; Robertson, A.; Hsu, H. F.; Weiss, R. G. Smectic liquid-crystalline phases of quaternary group VA (especially phosphonium) salts with three equivalent long n-alkyl chains. How do layered assemblies form in liquid-crystalline and crystalline phases. J. Am. Chem. Soc. 2000, 122, 3053–3062. doi: 10.1021/ja994055g
24. [24]
  Downard, A.; Earle, M. J.; Hardacre, C.; McMath, S. E. J.; Nieuwenhuyzen, M.; Teat, S. J. Structural studies of crystalline 1-alkyl-3-methylimidazolium chloride salts. Chem. Mater. 2004, 16, 43–48. doi: 10.1021/cm034344a
25. [25]
  Wang, A. J.; Zhao, Y.; Liu, X. M.; Chang, L. L.; Xuan, X. P. 1,3-Bis(carboxymethyl)imidazolium bis(trifluoromethylsulfonyl)imide organic salt: synthesis, single crystal structure, vibrational spectra, DFT calculations and physical-chemical properties. J. Fluorine Chem. 2016, 186, 7–11. doi: 10.1016/j.jfluchem.2016.04.003
26. [26]
  Wang, T. F.; Zheng, D. N.; Zhang, J. S.; Fan, B. W.; Ma, Y.; Ren, T. G.; Wang, L.; Zhang, J. L. Protic pyrazolium ionic liquids: an efficient catalyst for conversion of CO₂ in the absence of metal and solvent. ACS Sustain. Chem. Eng. 2018, 6, 2574–2582. doi: 10.1021/acssuschemeng.7b04051
27. [27]
  Ma, Y.; Zhang, Y.; Chen, C.; Zhang, J. S.; Fan, B. W.; Wang, T. F.; Ren, T. G.; Wang, L.; Zhang, J. L. Insight on asym-pyrazolium ionic liquids for chemical fixation of CO₂ and propylene epoxide into propylene arbonate without organic solvent and metal. Ind. Eng. Chem. Res. 2018, 57, 13342−13352. doi: 10.1021/acs.iecr.8b02318
28. [28]
  Ma, Y.; Chen, C.; Wang, T. F.; Zhang, J. S.; Wu, J. J.; Liu, X. D.; Ren, T. G.; Wang, L.; Zhang, J. L. Dialkylpyrazolium ionic liquids as novel catalyst for efficient fixation of CO₂ with metal- and solvent-free. Appl. Catal. A Gen. 2017, 547, 265–273. doi: 10.1016/j.apcata.2017.09.009
29. [29]
  Wang, T. F.; Zheng, D. N.; Ma, Y.; Guo, J. Y.; He, Z. P.; Ma, B.; Liu, L. H.; Ren, T. G.; Wang, L.; Zhang, J. L. Benzyl substituted imidazolium ionic liquids as efficient solvent-free catalysts for the cycloaddition of CO₂ with epoxides: experimental and theoretic study. J. CO₂ Util. 2017, 22, 44–52. doi: 10.1016/j.jcou.2017.09.009
30. [30]
  Sheldrick, G. M. A short history of SHELX. Acta Cryst A. 2008, 64, 112–122. doi: 10.1107/S0108767307043930
1. [1]
  Yao HUANG , Yingshu WU , Zhichun BAO , Yue HUANG , Shangfeng TANG , Ruixue LIU , Yancheng LIU , Hong LIANG . Copper complexes of anthrahydrazone bearing pyridyl side chain: Synthesis, crystal structure, anticancer activity, and DNA binding. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 213-224. doi: 10.11862/CJIC.20240359
2. [2]
  Jia JI , Zhaoyang GUO , Wenni LEI , Jiawei ZHENG , Haorong QIN , Jiahong YAN , Yinling HOU , Xiaoyan XIN , Wenmin WANG . Two dinuclear Gd(Ⅲ)-based complexes constructed by a multidentate diacylhydrazone ligand: Crystal structure, magnetocaloric effect, and biological activity. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 761-772. doi: 10.11862/CJIC.20240344
3. [3]
  Lu LIU , Huijie WANG , Haitong WANG , Ying LI . Crystal structure of a two-dimensional Cd(Ⅱ) complex and its fluorescence recognition of p-nitrophenol, tetracycline, 2, 6-dichloro-4-nitroaniline. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1180-1188. doi: 10.11862/CJIC.20230489
4. [4]
  Lulu DONG , Jie LIU , Hua YANG , Yupei FU , Hongli LIU , Xiaoli CHEN , Huali CUI , Lin LIU , Jijiang WANG . Synthesis, crystal structure, and fluorescence properties of Cd-based complex with pcu topology. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 809-820. doi: 10.11862/CJIC.20240171
5. [5]
  Xiumei LI , Yanju HUANG , Bo LIU , Yaru PAN . Syntheses, crystal structures, and quantum chemistry calculation of two Ni(Ⅱ) coordination polymers. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 2031-2039. doi: 10.11862/CJIC.20240109
6. [6]
  Xiumei LI , Linlin LI , Bo LIU , Yaru PAN . Syntheses, crystal structures, and characterizations of two cadmium(Ⅱ) coordination polymers. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 613-623. doi: 10.11862/CJIC.20240273
7. [7]
  Chao LIU , Jiang WU , Zhaolei JIN . Synthesis, crystal structures, and antibacterial activities of two zinc(Ⅱ) complexes bearing 5-phenyl-1H-pyrazole group. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1986-1994. doi: 10.11862/CJIC.20240153
8. [8]
  Xiaoxia WANG , Ya'nan GUO , Feng SU , Chun HAN , Long SUN . Synthesis, structure, and electrocatalytic oxygen reduction reaction properties of metal antimony-based chalcogenide clusters. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1201-1208. doi: 10.11862/CJIC.20230478
9. [9]
  Xiaoling WANG , Hongwu ZHANG , Daofu LIU . Synthesis, structure, and magnetic property of a cobalt(Ⅱ) complex based on pyridyl-substituted imino nitroxide radical. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 407-412. doi: 10.11862/CJIC.20240214
10. [10]
  Yan XU , Suzhi LI , Yan LI , Lushun FENG , Wentao SUN , Xinxing LI . Structure variation of cadmium naphthalene-diphosphonates with the changing rigidity of N-donor auxiliary ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 395-406. doi: 10.11862/CJIC.20240226
11. [11]
  Kaimin WANG , Xiong GU , Na DENG , Hongmei YU , Yanqin YE , Yulu MA . Synthesis, structure, fluorescence properties, and Hirshfeld surface analysis of three Zn(Ⅱ)/Cu(Ⅱ) complexes based on 5-(dimethylamino) isophthalic acid. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1397-1408. doi: 10.11862/CJIC.20240009
12. [12]
  Huan ZHANG , Jijiang WANG , Guang FAN , Long TANG , Erlin YUE , Chao BAI , Xiao WANG , Yuqi ZHANG . A highly stable cadmium(Ⅱ) metal-organic framework for detecting tetracycline and p-nitrophenol. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 646-654. doi: 10.11862/CJIC.20230291
13. [13]
  Ruikui YAN , Xiaoli CHEN , Miao CAI , Jing REN , Huali CUI , Hua YANG , Jijiang WANG . Design, synthesis, and fluorescence sensing performance of highly sensitive and multi-response lanthanide metal-organic frameworks. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 834-848. doi: 10.11862/CJIC.20230301
14. [14]
  Meirong HAN , Xiaoyang WEI , Sisi FENG , Yuting BAI . A zinc-based metal-organic framework for fluorescence detection of trace Cu²⁺. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1603-1614. doi: 10.11862/CJIC.20240150
15. [15]
  Shuyan ZHAO . Field-induced Co^Ⅱ single-ion magnet with pentagonal bipyramidal configuration. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1583-1591. doi: 10.11862/CJIC.20240231
16. [16]
  Yinling HOU , Jia JI , Hong YU , Xiaoyun BIAN , Xiaofen GUAN , Jing QIU , Shuyi REN , Ming FANG . A rhombic Dy₄-based complex showing remarkable single-molecule magnet behavior. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 605-612. doi: 10.11862/CJIC.20240251
17. [17]
  Daheng Wen , Weiwei Fang , Yongmei Liu , Tao Tu . Valorization of carbon dioxide with alcohols. Chinese Chemical Letters, 2024, 35(7): 109394-. doi: 10.1016/j.cclet.2023.109394
18. [18]
  Huiju Cao , Lei Shi . sp¹-Hybridized linear and cyclic carbon chain. Chinese Chemical Letters, 2025, 36(4): 110466-. doi: 10.1016/j.cclet.2024.110466
19. [19]
  Xiaowei TANG , Shiquan XIAO , Jingwen SUN , Yu ZHU , Xiaoting CHEN , Haiyan ZHANG . A zinc complex for the detection of anthrax biomarker. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1850-1860. doi: 10.11862/CJIC.20240173
20. [20]
  Hao-Cong Li , Ming Zhang , Qiyan Lv , Kai Sun , Xiao-Lan Chen , Lingbo Qu , Bing Yu . Homogeneous catalysis and heterogeneous separation: Ionic liquids as recyclable photocatalysts for hydroacylation of olefins. Chinese Chemical Letters, 2025, 36(2): 110579-. doi: 10.1016/j.cclet.2024.110579

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(398)
HTML views(21)

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

Synthesis, Crystal Structure of Protic Pyrazolium Ionic Liquid and Its Catalytic Properties for CO2 Cycloaddition

Metrics

通讯作者: 陈斌, bchen63@163.com

Synthesis, Crystal Structure of Protic Pyrazolium Ionic Liquid and Its Catalytic Properties for CO₂ Cycloaddition