Citation: 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[J]. Chinese Journal of Inorganic Chemistry, ;2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078 shu

Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction

College of Chemistry and Materials Engineering, Bohai University, Jinzhou, Liaoning 121013, China

Corresponding author: Min WANG, wangmin@qymail.bhu.edu.cn
Received Date: 11 March 2024
Revised Date: 18 June 2024

Figures(11)

Two supramolecular complexes of [Mn₂(2, 2′-bipy)₄(H₂O)Cl₃](L₁)·6H₂O (1) and [Mn(2, 2′-bipy)₂(H₂O)Cl](L₂)·3H₂O (2) (L₁^-=p-methylbenzenesulfonate anion, L₂^-=m-nitrobenzenesulfonate anion, 2, 2′-bipy=2, 2′-bipyridine) were synthesized by solvothermal method. The complexes were characterized by single-crystal X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, and nitrogen adsorption-desorption test. Using the Mannich reaction as a probe, the catalytic properties of the two complexes were studied, and the effects of the structure of the complexes on their catalytic properties were analyzed by comparing the results of scanning electron microscopy and powder X-ray diffraction. Finally, density functional theory was used to predict the active sites of the complexes, and X-ray photoelectron spectroscopy was used to prove the activation of the active sites. Then the mechanism of Mannich reaction catalyzed by the complexes was clarified.
- supramolecular complex,
- crystal structure,
- Mannich reaction,
- theoretical calculation,
- catalytic mechanism
1. [1]
  Pu M X, Guo H Y, Quan Z S, Li X T, Shen Q K. Application of the Mannich reaction in the structural modification of natural products[J]. J. Enzym. Inhib. Med. Chem., 2023,38(1):1-18.
2. [2]
  Kulkarni P. Sulfanilic acid catalysed one-pot three-component Mannich reaction for synthesis of β-amino ketones[J]. Vietnam J. Chem., 2020,58(5):675-687. doi: 10.1002/vjch.202000090
3. [3]
  Rani P, Prakash M, Samanta S. Organobase-catalyzed Mannich reaction of cyclic N-sulfonyl imines and 1, 2-diketones: A sustainable approach to 4-(3-arylquinoxalin-2-ylmethyl) sufamidates[J]. Tetrahedron Lett., 2023,122154490. doi: 10.1016/j.tetlet.2023.154490
4. [4]
  Mohurle S, Pasuparthy S D, Talamarla D, Kali V, Maiti B. [BCMIM][Cl] ionic liquid catalyzed diastereoselective synthesis of β-amino ketones via facile, one-pot, multicomponent Mannich reaction under solvent-free condition[J]. J. Heterocycl. Chem., 2023,60(9):1545-1557. doi: 10.1002/jhet.4698
5. [5]
  Azizi N, Edrisi M. Deep eutectic solvent immobilized on SBA-15 as a novel separable catalyst for one-pot three-component Mannich reaction[J]. Microporous Mesoporous Mat., 2017,240(11):130-136.
6. [6]
  Kalhor H R, Piraman Z, Fathali Y. Hen egg white lysozyme encapsulated in ZIF-8 for performing promiscuous enzymatic Mannich reaction[J]. iScience, 2023,26(10):1-21.
7. [7]
  Yang Z N, He H K, Tian R, Wu R R, Hu S, Wu Y, Zhou H. A zinc/ PyBisulidine catalyzed asymmetric Mannich reaction of N-tosyl imines with 3-acyloxy-2-oxindoles[J]. Org. Biomol. Chem., 2021,19(34):7460-7469. doi: 10.1039/D1OB01328A
8. [8]
  Mote N R, Chikkali S H. Hydrogen-bonding-assisted supramolecular metal catalysis[J]. Chem. Asian J., 2018,13(23):3623-3646. doi: 10.1002/asia.201801302
9. [9]
  Deng J H, Luo J, Mao Y L, Lai S, Gong Y N, Zhong D C, Lu T B. π-π stacking interactions: Non-negligible forces for stabilizing porous supramolecular frameworks[J]. Sci. Adv., 2020,6(2)eaax9976. doi: 10.1126/sciadv.aax9976
10. [10]
  Wang Y J, Wang M Y, Li Y B, Liu Q. Homogeneous manganese- catalyzed hydrogenation and dehydrogenation reactions[J]. Chem, 2021,7(5):1180-1223. doi: 10.1016/j.chempr.2020.11.013
11. [11]
  Liu C G, Wang M Y, Liu S H, Wang Y J, Peng Y, Lan Y, Liu Q. Manganese-catalyzed asymmetric hydrogenation of quinolines enabled by π-π interaction[J]. Angew. Chem. Int. Ed., 2021,60(10):5108-5113. doi: 10.1002/anie.202013540
12. [12]
  Zhang D P, Lan W L, Zhou Z, Yang L, Liu Q Y, Bian Y Z, Jiang J Z. Manganese(Ⅲ) porphyrin-based magnetic materials[J]. Top. Curr. Chem., 2019,377(18):1-43.
13. [13]
  Tao P, Liu S J, Wong W Y. Phosphorescent manganese(Ⅱ) complexes and their emerging applications[J]. Adv. Opt. Mater., 2020,8(20)2000985. doi: 10.1002/adom.202000985
14. [14]
  QI J Y, DANG X Y, ZHANG Y C, SONG Z G, WANG M. Study on the structure and catalytic property of two copper benzenesulfonate complexes[J]. Chemical Research and Application, 2022,34(11):2610-2618. doi: 10.3969/j.issn.1004-1656.2022.11.003
15. [15]
  Lin R B, Chen B. Hydrogen-bonded organic frameworks: Chemistry and functions[J]. Chem, 2022,8(8):2114-2135. doi: 10.1016/j.chempr.2022.06.015
16. [16]
  Bruker. SMART (Version 5.628), SAINT (Version 6.45), and SADABS. Bruker AXS Inc. : Madison, WI, 2001.
17. [17]
  Sheldrick G M. SHELXL-97, Program for the refinement of crystal structures. University of Göttingen, Germany, 1997.
18. [18]
  Wang C P, Wang Z, Mao S J, Chen Z R, Wang Y. Coordination environment of active sites and their effect on catalytic performance of heterogeneous catalysts[J]. Chin. J. Catal., 2022,43(4):928-955. doi: 10.1016/S1872-2067(21)63924-4
19. [19]
  Xie C, Yan D F, Li H, Du S Q, Chen W, Wang Y Y, Zou Y Q, Chen R, Wang S Y. Defect chemistry in heterogeneous catalysis: Recognition, understanding, and utilization[J]. ACS Catal., 2020,10(19):11082-11098. doi: 10.1021/acscatal.0c03034
20. [20]
  Han B, Wang H L, Wang C M, Wu H, Zhou W, Chen B L, Jiang J Z. Postsynthetic metalation of a robust hydrogen-bonded organic framework for heterogeneous catalysis[J]. J. Am. Chem. Soc., 2019,141(22):8737-8740. doi: 10.1021/jacs.9b03766
21. [21]
  XIA X, WANG S, YANG X Q, FAN R, WEI R Z, LIU Z, TANG Q. Synthesis, crystal structure and properties of zinc complex based on 2, 5-bis(trifluoromethyl) terephthalic acid ligand[J]. Chinese J. Inorg. Chem., 2021,37(12):2133-2140. doi: 10.11862/CJIC.2021.254
22. [22]
  Vassileva P, Krastev V, Lakov L, Peshev O. XPS determination of the binding energies of phosphorus and nitrogen in phosphazenes[J]. J. Mater. Sci., 2004,39(9):3201-3202. doi: 10.1023/B:JMSC.0000025859.82714.4a
23. [23]
  Neuvonen H, Neuvonen K, Koch A, Kleinpeter E, Pasanen P. Electron-withdrawing substituents decrease the electrophilicity of the carbonyl carbon. An investigation with the aid of ¹³C NMR chemical shifts, ν(C=O) frequency values, charge densities, and isodesmic reactions to interprete substituent effects on reactivity[J]. J. Org. Chem., 2002,67(20):6995-7003. doi: 10.1021/jo020121c
24. [24]
  Rakhtshah J, Ghaderi H, Yaghoobi F, Baghery S, Shaabani B. Synthesis of α-aminoalkyl naphthol derivatives in the presence of nickel complexes immobilized on multi-wall carbon nanotubes[J]. Mater. Chem. Phys., 2020,239121985. doi: 10.1016/j.matchemphys.2019.121985
1. [1]
  Yahui HAN , Jinjin ZHAO , Ning REN , Jianjun ZHANG . Synthesis, crystal structure, thermal decomposition mechanism, and fluorescence properties of benzoic acid and 4-hydroxy-2, 2′: 6′, 2″-terpyridine lanthanide complexes. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 969-982. doi: 10.11862/CJIC.20240395
2. [2]
  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
3. [3]
  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
4. [4]
  Jing WU , Puzhen HUI , Huilin ZHENG , Pingchuan YUAN , Chunfei WANG , Hui WANG , Xiaoxia GU . Synthesis, crystal structures, and antitumor activities of transition metal complexes incorporating a naphthol-aldehyde Schiff base ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2422-2428. doi: 10.11862/CJIC.20240278
5. [5]
  Hongjie SHEN , Haozhe MIAO , Yuhe YANG , Yinghua LI , Deguang HUANG , Xiaofeng ZHANG . Synthesis, crystal structure, and fluorescence properties of two Cu(Ⅰ) complexes based on pyridyl ligand. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 855-863. doi: 10.11862/CJIC.20250009
6. [6]
  Wenyan Dan , Weijie Li , Xiaogang Wang . The Technical Analysis of Visual Software ShelXle for Refinement of Small Molecular Crystal Structure. University Chemistry, 2024, 39(3): 63-69. doi: 10.3866/PKU.DXHX202302060
7. [7]
  Xinting XIONG , Zhiqiang XIONG , Panlei XIAO , Xuliang NIE , Xiuying SONG , Xiuguang YI . Synthesis, crystal structures, Hirshfeld surface analysis, and antifungal activity of two complexes Na(Ⅰ)/Cd(Ⅱ) assembled by 5-bromo-2-hydroxybenzoic acid ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1661-1670. doi: 10.11862/CJIC.20240145
8. [8]
  Hexing SONG , Zan SUN . Synthesis, crystal structure, Hirshfeld surface analysis, and fluorescent sensing for Fe³⁺ of an Mn(Ⅱ) complex based on 1-naphthalic acid. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 885-892. doi: 10.11862/CJIC.20240402
9. [9]
  Longfei MA , Fang SI , Congjie PAN , Xinhua WANG . Synthesis and crystal structure of extended tetrathiafulvalene derivatives and cupric bromide charge transfer complexes. Chinese Journal of Inorganic Chemistry, 2026, 42(6): 1229-1236. doi: 10.11862/CJIC.20250355
10. [10]
  Yuxin CHEN , Yanni LING , Yuqing YAO , Keyi WANG , Linna LI , Xin ZHANG , Qin WANG , Hongdao LI , Wenmin WANG . Construction, structures, and interaction with DNA of two Sm^Ⅲ₄ complexes. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1141-1150. doi: 10.11862/CJIC.20240258
11. [11]
  Chengyan XU , Jiangnan YU , Yu LI , Xizhen PAN , Yinlin HOU , Wenmin WANG . Synthesis, structure, and bioactivity of a Ho₄ complex bridged by azide group. Chinese Journal of Inorganic Chemistry, 2026, 42(7): 1453-1462. doi: 10.11862/CJIC.20260033
12. [12]
  Linjie ZHU , Xufeng LIU . Electrocatalytic hydrogen evolution performance of tetra-iron complexes with bridging diphosphine ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 321-328. doi: 10.11862/CJIC.20240207
13. [13]
  Jingjing QING , Fan HE , Zhihui LIU , Shuaipeng HOU , Ya LIU , Yifan JIANG , Mengting TAN , Lifang HE , Fuxing ZHANG , Xiaoming ZHU . Synthesis, structure, and anticancer activity of two complexes of dimethylglyoxime organotin. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1301-1308. doi: 10.11862/CJIC.20240003
14. [14]
  Jia JI , Tengqi YAO , Wenqian DENG , Wenjing SHI , Xuan LÜ , Lin TIAN , Xiaoyan XIN , Yinling HOU . Structures, antibacterial activities, and interactions with DNA of two nickel complexes. Chinese Journal of Inorganic Chemistry, 2026, 42(1): 78-86. doi: 10.11862/CJIC.20250141
15. [15]
  Wenjuan SHI , Yuxuan LEI , Lei HOU , Yaoyu WANG . Synthesis, structure, and luminescence properties of trinucluear Cu(Ⅰ)-pyrazole complexes containing different substituent groups. Chinese Journal of Inorganic Chemistry, 2026, 42(3): 543-550. doi: 10.11862/CJIC.20250270
16. [16]
  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
17. [17]
  Linjie ZHU , Xufeng LIU . Synthesis, characterization and electrocatalytic hydrogen evolution of two di-iron complexes containing a phosphine ligand with a pendant amine. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 939-947. doi: 10.11862/CJIC.20240416
18. [18]
  Liu Lin , Zemin Sun , Huatian Chen , Lian Zhao , Mingyue Sun , Yitao Yang , Zhensheng Liao , Xinyu Wu , Xinxin Li , Cheng Tang . Recent Advances in Electrocatalytic Two-Electron Water Oxidation for Green H₂O₂ Production. Acta Physico-Chimica Sinica, 2024, 40(4): 2305019-0. doi: 10.3866/PKU.WHXB202305019
19. [19]
  Lifang HE , Wenjie TANG , Yaoze LUO , Mingsheng LIANG , Jianxin TANG , Yuxuan WU , Fuxing ZHANG , Xiaoming ZHU . Synthesis, structure, and anticancer activity of two dialkyltin complexes constructed based on 2, 2′-bipyridin-6, 6′-dicarboxylic acid. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1601-1609. doi: 10.11862/CJIC.20250012
20. [20]
  Xuhu GUO , Chuntao ZHANG , Jinshu LI , Yuanyuan TAN , Qaiowen CHANG , Juan YU . Structure and catalytic performance of [Pd(1, 5-cyclooctadiene)X₂] (X=Cl, Br) modulated by organophosphine ligands. Chinese Journal of Inorganic Chemistry, 2026, 42(6): 1247-1260. doi: 10.11862/CJIC.20250299

Get Citation

PDF

XML

Metrics

PDF Downloads(19)
Abstract views(3258)
HTML views(449)

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