Citation: WANG Qing, MA Cheng-Bing, CHEN Hui, HUANG De-Guang, CHEN Chang-Neng. Five-heterocyclic-biphosphinesubstituted Fe-only Hydrogenase Mimic: Synthesis, Characterization and Properties[J]. Chinese Journal of Structural Chemistry, ;2016, 35(12): 1972-1979. doi: 10.14102/j.cnki.0254-5861.2011-1211 shu

Five-heterocyclic-biphosphinesubstituted Fe-only Hydrogenase Mimic: Synthesis, Characterization and Properties

a.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
b.
University of Chinese Academy of Sciences, Beijing 100039, China

Corresponding author: CHEN Chang-Neng, ccn@fjirsm.ac.cn
Received Date: 22 March 2016
Accepted Date: 2 June 2016

Fund Project: the NNSFC 21231003 and 21203195

Figures(4)

A new five-heterocyclic-biphosphine-substituted Fe-only hydrogenase mimic,[(μ-pdt)Fe₂(CO)₅]₂(PTP) (1), has been synthesized at room temperature. 1·H₂O crystallizes in triclinic system, space group P1, with a=11.5897(4), b=13.6156(4), c=18.0333(6)Å, α=76.306(3), β=72.742(3), γ=68.939(3)°, V=2508.84(14)Å³, D_c=1.570 g/cm³, Z=2, M_r=1186.37, F(000)=1204, the final R=0.0748, and wR=0.2012. In the tetranuclear complex 1·H₂O, each[2Fe2S] butterfly unit is attached to one P atom of the diphosphine bridge and exhibits a square-pyramidal geometry. Complex 1 was characterized by elemental analysis, IR spectra, UV-vis absorption spectra, ¹H-NMR and ³¹P-NMR. The cyclic voltammetry behavior of compound 1 was investigated as well.
- Fe-only hydrogenase mimic,
- spectral analysis,
- cyclic voltammetry
1. [1]
  Lawrence J. D, Li H, Rauchfuss T. B, Benard M, Rohmer M. M. Diiron azadithiolates as models for the iron-only hydrogenase active site: synthesis, structure, and stereoelectronics[J]. Angew. Chem., Int. Ed., 2001,40:1768-1771. doi: 10.1002/(ISSN)1521-3773
2. [2]
  Ott S, Kritikos M, Akermark B, Sun L C, Lomoth R. A biomimetic pathway for hydrogen evolution from a model of the iron hydrogenase active site[J]. Angew. Chem., Int. Ed., 2004,43:1006-1009. doi: 10.1002/(ISSN)1521-3773
3. [3]
  Felton G. A. N, Mebi C. A, Petro B. J, Vannucci A. K, Evans D. H, Glass R. S, Lichtenberger D. L. Review of electrochemical studies of complexes containing the Fe2S2 core characteristic of[J]. J. Organomet. Chem., 2009,694:2681-2699. doi: 10.1016/j.jorganchem.2009.03.017
4. [4]
  Baltazar C. S. A, Marques M. C, Soares C. M, DeLacey A. M, Pereira I. A. C, Matias P. M. Nickel-iron-selenium hydrogenases-an overview[J]. Eur. J. Inorg. Chem., 2011,7:948-962.
5. [5]
  Frey, M. Hydrogenases: hydrogen-activating enzymes. ChemBioChem. 2002, 2-3, 153-160.
6. [6]
  Peters J. W, Lanzilotta W. N, Lemon B. J, Seefeldt L. C. X-ray crystal structure of the Fe-only hydrogenase (CpI) from Clostridium pasteurianum to 1.8 angstrom resolution[J]. Science, 1998,282:1853-1858. doi: 10.1126/science.282.5395.1853
7. [7]
  Peters J. W. Structure and mechanism of iron-only hydrogenases[J]. Curr. Opin. Struc. Biol., 1999,9:670-676. doi: 10.1016/S0959-440X(99)00028-7
8. [8]
  Huo F. W, Hou J, Chen G. C, Guo D. M, Peng X. J. [FeFe]-Hydrogen models: overpotential control for electrocatalytic H2 production by tuning of the ligand π-acceptor ability. Eur. J[J]. Inorg. Chem., 2010,25:3942-3951.
9. [9]
  Chong D, Georgakaki I. P, Mejia-Rodriguez R, Sanabria-Chinchilla J, Soriaga M. P, Darensbourg M. Y. Electrocatalysis of hydrogen production by active site analogues of the iron hydrogenase enzyme: structure/function relationships[J]. Dalton Trans., 2003,21:4158-4163.
10. [10]
  Schwartz L, Eilers G, Eriksson L, Gogoll A, Lomoth R, Ott S. Iron hydrogenase active site mimic holding a proton and a hydride[J]. Chem. Commun., 2006,5:520-522.
11. [11]
  Si G, Wang W. G, Wang H. Y, Tung C. H, Wu L. Z. Facile synthesis and functionality-dependent electrochemistry of Fe-only hydrogenase mimics[J]. Inorg. Chem., 2008,47:8101-8111. doi: 10.1021/ic800676y
12. [12]
  Gloaguen F, Lawrence J. D, Rauchfuss T. B, Benard M, Rohmer M. M. Bimetallic carbonyl thiolates as functional models for Fe-only hydrogenases[J]. Inorg. Chem., 2002,41:6573-6582. doi: 10.1021/ic025838x
13. [13]
  Gloaguen F, Lawrence J. D, Rauchfuss T. B. Biomimetic hydrogen evolution catalyzed by an iron carbonyl thiolate[J]. J. Am. Chem. Soc., 2001,123:9476-9477. doi: 10.1021/ja016516f
14. [14]
  Chong D. S, Georgakaki I. P, Mejia-Rodriguez R, Samabria-Chinchilla J, Soriaga M. P, Darensbourg M. Y. Electrocatalysis of hydrogen production by active site analogues of the iron hydrogenase enzyme: structure /function relationships[J]. Dalton Trans., 2003,21:4158-4163.
15. [15]
  Capon J. F, Gloaguen F, Schollhammer P, Talarmin J. Electrochemical proton reduction by thiolate-bridged hexacarbonyldiiron clusters[J]. J. Electroanal. Chem., 2004,566:241-247. doi: 10.1016/j.jelechem.2003.11.032
16. [16]
  Song L. C, Yang Z, Bian H. Z, Hu Q. M. Novel single and double diiron oxadithiolates as models for the active site of[J]. Organometallics, 2004,13:3082-3084.
17. [17]
  Si Y, Charreteur K, Capon J. F, Gloaguen F. Pétillon, F. Y, Schollhammer, P. Talarmin, J. Non-innocent bma ligand in a dissymetrically disubstituted diiron dithiolate related to the active site of the[J]. J. Inorg. Biochem., 2010,104:1038-1042. doi: 10.1016/j.jinorgbio.2010.05.011
18. [18]
  Cui H. H, Wu N. N, Wang J. Y, Hu M. Q, Wen H. M, Chen C. N. Pyridyl- and pyrimidyl-phosphine-substituted[J]. J. Organomet. Chem., 2014,767:46-53. doi: 10.1016/j.jorganchem.2014.04.026
19. [19]
  Capon J. F, Gloaguen F, Schollhammer P, Talarmin J. Activation of proton by the two-electron reduction of a di-iron organometallic complex[J]. J. Electroanal. Chem., 2006,595:47-52. doi: 10.1016/j.jelechem.2006.06.005
20. [20]
  Felton G. A. N, Vannucci A. K, Chen J. Z, Lockett L. T, Okumura N, Petro B. J, Zakai U. I, Evans D. H, Glass R. S, Lichtenberger D. L. Hydrogen generation from weak acids: electrochemical and computational studies of a diiron hydrogenase mimic[J]. J. Am. Chem. Soc., 2007,41:12521-12530.
21. [21]
  Chen L, Wang M, Gloaguen F, Zheng D. H, Zhang P. L, Sun L. C. Multielectron-transfer templates via consecutive two-electron transformations: iron-sulfur complexes relevant to biological enzymes[J]. Chem. Eur. J., 2012,18:13968-13973. doi: 10.1002/chem.v18.44
22. [22]
  Chen L, Wang M, Gloaguen F, Zheng D. H, Zhang P. L, Sun L. C. Tetranuclear iron complexes bearing benzenetetrathiolate bridges as four-electron transformation templates and their electrocatalytic properties for proton reduction[J]. Inorg. Chem., 2013,52:1798-1806. doi: 10.1021/ic301647u
23. [23]
  Kang D. M, Kim S. G, Lee S. J, Park J. K, Park K. M, Shin S. C. Synthesis, characterization, and absorption spectra of metallamacrocycles,[J]. Soc., 2005,9:1390-1394.
24. [24]
  Sevillano P, Fuhr O, Hampe O, Lebedkin S, Neiss C, Ahlrichs R, Fenske D, Kappes M. M. Synthesis, characterization and quantum mechanical calculations of[J]. J. Inorg. Chem., 2007,33:5163-5167.
25. [25]
  Stott T. L, Wolf M. O, Patrick B. O. Structural and electronic properties of phosphino(oligothiophene) gold(I) complexes[J]. Inorg. Chem., 2005,3:620-627.
26. [26]
  Brown, J. M.; Lucy, A. R. Trans-bis(diphenylphosphino)cyclopropane; a ligand selective for binuclear complexation with ca. 4.5 ? intermetallic separation. J. Organomet. Chem. 1986, 1-2, 241-246.
27. [27]
  Hourihane R, Gray G, Spalding T, Deeney T. Synthesis and spectroscopic characterisation of compounds with formula[J]. Chem., 2002,642:40-47.
28. [28]
  Li P, Wang M, He C. J, Li G. H, Liu X. Y, Chen C. N, Akermark B, Sun L. C. Influence of tertiary phosphanes on the coordination configurations and electrochemical properties of iron hydrogenase model complexes: crystal structures of[J]. J. Inorg. Chem., 2005,12:2506-2513.
29. [29]
  Messelhauser J, Lorenz I. P, Haug K, Hiller W. Synthesis and structure of the ethenedithiolato complex[J]. Z. Naturforsch Teil. B, 1985,40:1064-1067.
30. [30]
  Stott T. L, Wolf M. O. Spectroscopic study of phosphine-substituted oligothiophenes[J]. J. Phys. Chem. B, 2004,108:18815-18819. doi: 10.1021/jp047037g
31. [31]
  Sheldrick, G. M. SHELXS97, Program for the Solution of Crystal Structure. University of G?ttingen, Germany 1997.
32. [32]
  Sheldrick, G. M. SHELXL97, Program for the Refinement of Crystal Structure. University of G?ttingen, Germany 1997.
33. [33]
  Zhao X; Georgakaki I. P, Miller M. L, Mejia-Rodriguez R, Chiang C. Y, Darensbourg M. Y. Catalysis of H2/D2 scrambling and other H/D exchange processes by[J]. Inorg. Chem., 2002,15:3917-3928.
34. [34]
  Ott S, Borgstrom M, Kritikos M, Lomoth R, Bergquist J, Akermark B, Hammarstrom L, Sun L. C. Model of the iron hydrogenase active site covalently linked to a ruthenium photosensitizer: synthesis and photophysical properties[J]. Inorg. Chem., 2004,15:4683-4692.
35. [35]
  Gloaguen F, Lawrence J. D, Rauchfuss T. B, Benard M, Rohmer M. M. Bimetallic carbonyl thiolates as functional models for Fe-Only hydrogenases[J]. Inorg. Chem., 2002,25:6573-6582.
36. [36]
  Gao W. M, Liu J. H, Akermark B, Sun L. C. Bidentate phosphine ligand based Fe2S2-containing macromolecules: synthesis, characterization, and catalytic electrochemical hydrogen production[J]. Inorg. Chem., 2006,23:9169-9171.
37. [37]
  Matthews S. L, Heinekey D. M. A carbonyl-rich bridging hydride complex relevant to the Fe-Fe hydrogenase active site[J]. Inorg. Chem., 2010,49:9746-9748. doi: 10.1021/ic1017328
38. [38]
  Gao W. M, Ekstrom J, Liu J. H, Chen C. N, Eriksson L, Weng L. H, Akermark B, Sun L. H. Binuclear iron-sulfur complexes with bidentate phosphine ligands as active site models of Fe-hydrogenase and their catalytic proton reduction[J]. Inorg. Chem., 2007,46:1981-1991. doi: 10.1021/ic0610278
1. [1]
  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
2. [2]
  Kai An , Qinglong Qiao , Lovelesh , Syed Ali Abbas Abedi , Xiaogang Liu , Zhaochao Xu . "Superimposed" spectral characteristics of fluorophores arising from cross-conjugation hybridization. Chinese Chemical Letters, 2025, 36(1): 109786-. doi: 10.1016/j.cclet.2024.109786
3. [3]
  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
4. [4]
  Zhangyong LIU , Lihui XU , Yue YANG , Liming WANG , Hong PAN , Xinzhe HUANG , Xueqiang FU , Yingxiu ZHANG , Meiran DOU , Meng WANG , Yi TENG . Preparation and photocatalytic performance of Cs_xWO₃/TiO₂ based on full spectral response. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1445-1464. doi: 10.11862/CJIC.20240345
5. [5]
  Yi Liu , Peng Lei , Yang Feng , Shiwei Fu , Xiaoqing Liu , Siqi Zhang , Bin Tu , Chen Chen , Yifan Li , Lei Wang , Qing-Dao Zeng . Topologically engineering of π-conjugated macrocycles: Tunable emission and photochemical reaction toward multi-cyclic polymers. Chinese Chemical Letters, 2024, 35(10): 109571-. doi: 10.1016/j.cclet.2024.109571
6. [6]
  Junxin Li , Chao Chen , Yuzhen Dong , Jian Lv , Jun-Mei Peng , Yuan-Ye Jiang , Daoshan Yang . Ligand-promoted reductive coupling between aryl iodides and cyclic sulfonium salts by nickel catalysis. Chinese Chemical Letters, 2024, 35(11): 109732-. doi: 10.1016/j.cclet.2024.109732
7. [7]
  Xueling Yu , Lixing Fu , Tong Wang , Zhixin Liu , Na Niu , Ligang Chen . Multivariate chemical analysis: From sensors to sensor arrays. Chinese Chemical Letters, 2024, 35(7): 109167-. doi: 10.1016/j.cclet.2023.109167
8. [8]
  Shulei Hu , Yu Zhang , Xiong Xie , Luhan Li , Kaixian Chen , Hong Liu , Jiang Wang . Rh(Ⅲ)-catalyzed late-stage C-H alkenylation and macrolactamization for the synthesis of cyclic peptides with unique Trp(C7)-alkene crosslinks. Chinese Chemical Letters, 2024, 35(8): 109408-. doi: 10.1016/j.cclet.2023.109408
9. [9]
  Feng Zhao , Hongyu Ding , Ting Sun , Chao Shen , Zu-Li Wang , Wei Wei , Dong Yi . Visible-light-promoted multi-component carbene transfer reactions of diazo compounds via ring-opening of cyclic ethers. Chinese Chemical Letters, 2026, 37(2): 111834-. doi: 10.1016/j.cclet.2025.111834
10. [10]
  Neng Shi , Haonan Jia , Jixiang Zhang , Pengyu Lu , Chenglong Cai , Yixin Zhang , Liqiang Zhang , Nongyue He , Weiran Zhu , Yan Cai , Zhangqi Feng , Ting Wang . Accurate expression of neck motion signal by piezoelectric sensor data analysis. Chinese Chemical Letters, 2024, 35(9): 109302-. doi: 10.1016/j.cclet.2023.109302
11. [11]
  Yuxin Li , Chengbin Liu , Qiuju Li , Shun Mao . Fluorescence analysis of antibiotics and antibiotic-resistance genes in the environment: A mini review. Chinese Chemical Letters, 2024, 35(10): 109541-. doi: 10.1016/j.cclet.2024.109541
12. [12]
  Zixuan Chen , Yafeng Wu , Zhaoyan Tian , Zhaohan Wang , Weiwei Liu , Songqin Liu . A reproducible hybrid membrane for in situ analysis of cell secretions with a wide size range. Chinese Chemical Letters, 2025, 36(12): 110917-. doi: 10.1016/j.cclet.2025.110917
13. [13]
  Zihe SONG , Jinjin ZHAO , Ning REN , Jianjun ZHANG . Crystal structure, thermal analysis, and luminescence properties of six heterocyclic lanthanide complexes. Chinese Journal of Inorganic Chemistry, 2026, 42(1): 181-192. doi: 10.11862/CJIC.20250126
14. [14]
  Chuanjian Cui , Zhuang Liu , Shiyu Yang , Qiang Wei , Jiahui Ding , Ziyang Xu , Changyong Zhang . Performance analysis of membrane capacitive deionization (MCDI): The relative insensitivity to feedwater temperatures. Chinese Chemical Letters, 2026, 37(2): 111342-. doi: 10.1016/j.cclet.2025.111342
15. [15]
  Yanhui Zhong , Peisi Xie , Chengyi Xie , Lei Guo , Weiwei Chen , Shuyi Wang , Xiaoxiao Wang , Fuyue Wang , Zian Lin , Gongke Li , Zongwei Cai . Rigid urea-based structures drive analysis of chiral amino acids. Chinese Chemical Letters, 2026, 37(2): 112039-. doi: 10.1016/j.cclet.2025.112039
16. [16]
  Mingying Chen , Junjie Ma , Xiyong Chen , Qian Liu , Yanhong Feng , Xijun Liu . Support engineering of single-atom electrocatalysis: Mechanism analysis and application expansion. Chinese Chemical Letters, 2026, 37(4): 111637-. doi: 10.1016/j.cclet.2025.111637
17. [17]
  Xiaohui Fu , Yanping Zhang , Juan Liao , Zhen-Hua Wang , Yong You , Jian-Qiang Zhao , Mingqiang Zhou , Wei-Cheng Yuan . Palladium-catalyzed enantioselective decarboxylation of vinyl cyclic carbamates: Generation of amide-based aza-1,3-dipoles and application to asymmetric 1,3-dipolar cycloaddition. Chinese Chemical Letters, 2024, 35(12): 109688-. doi: 10.1016/j.cclet.2024.109688
18. [18]
  Tian Feng , Yun-Ling Gao , Di Hu , Ke-Yu Yuan , Shu-Yi Gu , Yao-Hua Gu , Si-Yu Yu , Jun Xiong , Yu-Qi Feng , Jie Wang , Bi-Feng Yuan . Chronic sleep deprivation induces alterations in DNA and RNA modifications by liquid chromatography-mass spectrometry analysis. Chinese Chemical Letters, 2024, 35(8): 109259-. doi: 10.1016/j.cclet.2023.109259
19. [19]
  Cheng Guo , Xiaoxiao Zhang , Xiujuan Hong , Yiqiu Hu , Lingna Mao , Kezhi Jiang . Graphene as adsorbent for highly efficient extraction of modified nucleosides in urine prior to liquid chromatography-tandem mass spectrometry analysis. Chinese Chemical Letters, 2024, 35(4): 108867-. doi: 10.1016/j.cclet.2023.108867
20. [20]
  Keqiang Shi , Xiujuan Hong , Dongyan Xu , Tao Pan , Huiwen Wang , Hongru Feng , Cheng Guo , Yuanjiang Pan . Analysis of RNA modifications in peripheral white blood cells from breast cancer patients by mass spectrometry. Chinese Chemical Letters, 2025, 36(3): 110079-. doi: 10.1016/j.cclet.2024.110079

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(4636)
HTML views(108)

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