Citation:
XU Fen-Fena, FENG Ya-Nan, DU Shao-Wu, CHEN Yi-Feng. A New Pyridine-substituted Azadithiolate 2Fe2S Complex Related to the Active Site of [FeFe]-hydrogenase[J]. Chinese Journal of Structural Chemistry,
;2016, 35(2): 237-245.
doi:
10.14102/j.cnki.0254-5861.2011-0995
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A new 2Fe2S complex [(2-C5H4N)N(μ-CH2S)2Fe2(CO)6] (1) related to the active site of [FeFe]-hydrogenase was obtained by treating (HS)2Fe2(CO)6 with (pyridin-2-ylazanediyl) dimethanol. Protonation occurred at the pyridine nitrogen atom when two equivalents of HBF4·OEt2 acid were added to the toluene solution of 1, leading to the formation of [(2-C5H4NH)N(μ- CH2S)2Fe2(CO)6]·BF4·OEt2 (1H+), whose molecular structure was further established by single- crystal X-ray analysis. Complex 1 crystallizes in the monoclinic system, space group P21/n with a = 7.728(3), b = 11.825(4), c = 17.888(6) Å, β = 92.968(5)°, while complex 1H+ crystallizes in the triclinic system, space group P1 with a = 7.672(4), b = 10.382(5), c = 16.480(10) Å, α = 106.575(13), β = 93.18(3), γ = 104.262(17)°.
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-
[1]
(1) Tard, C.; Pickett, C. J. Structural and functional analogues of the active sites of the Fe-, NiFe-, and FeFe-hydrogenases. Chem. Rev. 2009, 109, 2245-2274.
-
[2]
(2) Mulder, D. W.; Shepard, E. M.; Meuser, J. E.; Joshi, N.; King, P. W.; Posewitz, M. C.; Broderick, J. B.; Peters, J. W. Insights into FeFe-hydrogenase structure, mechanism, and maturation. Structure 2011, 19, 1038-1052.
-
[3]
(3) Nicolet, Y.; Fontecilla-Camps, J. C. Structure-function relationships in FeFe-hydrogenase active site maturation. J. Biol. Chem. 2012, 287, 13532-13540.
-
[4]
(4) Broderick, J. B.; Byer, A. S.; Duschene, K. S.; Duffus, B. R.; Betz, J. N.; Shepard, E. M.; Peters, J. W. H-Cluster assembly during maturation of the FeFe-hydrogenase. J. Biol. Inorg. Chem. 2014, 19, 747-757.
-
[5]
(5) Lubitz, W.; Ogata, H.; Rüdiger, O.; Reijerse, E. Hydrogenases. Chem. Rev. 2014, 114, 4081-4148.
-
[6]
(6) Peters, J. W.; Lanzilotta, W. N.; Lemon, B. J.; Seefeldt, L. C. X-ray crystal structure of the Fe-only hydrogenase (Cpl) from clostridium pasteurianum to 1.8 angstrom resolution. Science 1998, 282, 1853-1858.
-
[7]
(7) Nicolet, Y.; Piras, C.; Legrand, P.; Hatchikian, C. E.; Fontecilla-Camps, J. C. Desulfovibrio desulfuricans iron hydrogenase: the structure shows unusual coordination to an active site Fe binuclear center. Structure 1999, 7, 13-23.
-
[8]
(8) Tard, C.; Liu, X. M.; Ibrahim, S. K.; Bruschi, M.; De Gioia, L.; Davies, S. C.; Yang, X.; Wang, L. S.; Sawers, G.; Pickett, C. J. Synthesis of the H-cluster framework of iron-only hydrogenase. Nature 2005, 433, 610-613.
-
[9]
(9) Song, L. C. Investigations on butterfly Fe/S cluster S-centered anions (m-S-)2Fe2(CO)6, (m-S-)(m-RS)Fe2(CO)6, and related species. Acc. Chem. Res. 2005, 38, 21-28.
-
[10]
(10) Liu, X. M.; Ibrahim, S. K.; Tard, C.; Pickett, C. J. Iron-only hydrogenase: synthetic, structural and reactivity studies of model compounds. Coord. Chem. Rev. 2005, 249, 1641-1652.
-
[11]
(11) Sun, L. C.; Akermark, B.; Ott, S. Iron hydrogenase active site mimics in supramolecular systems aiming for light-driven hydrogen production. Coord. Chem. Rev. 2005, 249, 1653-1663.
-
[12]
(12) 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 FeFe-hydrogenases including catalysis by these complexes of the reduction of acids to form dihydrogen. J. Organomet. Chem. 2009, 694, 2681-2699.
-
[13]
(13) Wang, Y.; Li, Z.; Zeng, X.; Wang, X.; Zhan, C.; Liu, Y.; Zeng, X.; Luo, Q.; Liu, X. Synthesis and characterisation of three diiron tetracarbonyl complexes related to the diiron centre of FeFe-hydrogenase and their protonating, electrochemical investigations. New J. Chem. 2009, 33, 1780-1789.
-
[14]
(14) Zeng, X.; Li, Z.; Xiao, Z.; Wang, Y.; Liu, X. Using pendant ferrocenyl group(s) as an intramolecular standard to probe the reduction of diiron hexacarbonyl model complexes for the sub-unit of FeFe -hydrogenase. Electrochem. Commun. 2010, 12, 342-345.
-
[15]
(15) Zhong, W.; Tang, Y.; Zampella, G.; Wang, X.; Yang, X.; Hu, B.; Wang, J.; Xiao, Z.; Wei, Z.; Chen, H.; De Gioia, L.; Liu, X. A rare bond between a soft metal (Fe-l) and a relatively hard base (RO-, R = phenolic moiety). Inorg. Chem. Commun. 2010, 13, 1089-1092.
-
[16]
(16) Xiao, Z. Y.; Wei, Z. H.; Long, L.; Wang, Y. L.; Evans, D. J.; Liu, X. M. Diiron carbonyl complexes possessing a {Fe(II)Fe(II)} core: synthesis, characterisation, and electrochemical investigation. Dalton Trans. 2011, 40, 4291-4299.
-
[17]
(17) Tang, Y.; Wei, Z.; Zhong, W.; Liu, X. Diiron complexes with pendant phenol group(s) as mimics of the diiron subunit of FeFe-hydrogenase: synthesis, characterisation, and electrochemical investigation. Eur. J. Inorg. Chem. 2011, 1112-1120.
-
[18]
(18) Long, L.; Xiao, Z. Y.; Zampella, G.; Wei, Z. H.; De Gioia, L.; Liu, X. M. The reactions of pyridinyl thioesters with triiron dodecacarbonyl: their novel diiron carbonyl complexes and mechanistic investigations. Dalton Trans. 2012, 41, 9482-9492.
-
[19]
(19) Wu, L. Z.; Chen, B.; Li, Z. J.; Tung, C. H. Enhancement of the efficiency of photocatalytic reduction of protons to hydrogen via molecular assembly. Acc. Chem. Res. 2014, 47, 2177-2185.
-
[20]
(20) Qian, G.; Wang, H.; Zhong, W.; Liu, X. Electrochemical investigation into the electron transfer mechanism of a diiron hexacarbonyl complex bearing a bridging naphthalene moiety. Electrochim. Acta 2015, 163, 190-195.
-
[21]
(21) Pulukkody, R.; Darensbourg, M. Y. Synthetic advances inspired by the bioactive dinitrosyl iron unit. Acc. Chem. Res. 2015, 48, 2049-2058.
-
[22]
(22) Artero, V.; Berggren, G.; Atta, M.; Caserta, G.; Roy, S.; Pecqueur, L.; Fontecave, M. From enzyme maturation to synthetic chemistry: the case of hydrogenases. Acc. Chem. Res. 2015, 48, 2380-2387.
-
[23]
(23) Zhu, D.; Xiao, Z.; Liu, X. Introducing polyethyleneimine (PEI) into the electrospun fibrous membranes containing diiron mimics of [FeFe]-hydrogenase: Membrane electrodes and their electrocatalysis on proton reduction in aqueous media. Int. J. Hydrogen Energy 2015, 40, 5081-5091.
-
[24]
(24) Rauchfuss, T. B. Diiron azadithiolates as models for the FeFe-hydrogenase active site and paradigm for the role of the second coordination sphere. Acc. Chem. Res. 2015, 48, 2107-2116.
-
[25]
(25) Capon, J. F.; Gloaguen, F.; Petillon, F. Y.; Schollhammer, P.; Talarmin, J. Electron and proton transfers at diiron dithiolate sites relevant to the catalysis of proton reduction by the FeFe-hydrogenases. Coord. Chem. Rev. 2009, 253, 1476-1494.
-
[26]
(26) Song, L. C.; Ge, J. H.; Liu, X. F.; Zhao, L. Q.; Hu, Q. M. Synthesis, structure and electrochemical properties of N-substituted diiron azadithiolates as active site models of Fe-only hydrogenases. J. Organomet. Chem. 2006, 691, 5701-5709.
-
[27]
(27) Lawrence, J. D.; Li, H.; Rauchfuss, T. B. Beyond Fe-only hydrogenases: N-functionalized 2-aza-1,3-dithiolates Fe[(SCH)NR](CO)x (x = 5, 6). Chem. Commun. 2001, 1482-1483.
-
[28]
(28) Jiang, S.; Liu, J. H.; Sun, L. C. A furan-containing diiron azadithiolate hexacarbonyl complex with unusual lower catalytic proton reduction potential. Inorg. Chem. Commun. 2006, 9, 290-292.
-
[29]
(29) Jiang, S.; Liu, J. H.; Shi, Y.; Wang, Z.; Akermark, B.; Sun, L. H. Preparation, characteristics and crystal structures of novel N-heterocyclic carbene substituted furan- and pyridine-containing azadithiolate Fe-S complexes. Polyhedron 2007, 26, 1499-1504.
-
[30]
(30) Jiang, S.; Liu, J. H.; Shi, Y.; Wang, Z.; Akermark, B.; Sun, L. C. Fe-S complexes containing five-membered heterocycles: novel models for the active site of hydrogenases with unusual low reduction potential. Dalton Trans. 2007, 896-902.
-
[31]
(31) Sheldrick, G. M. SADABS. University of Göttingen: Germany 1996.
-
[32]
(32) Sheldrick, G. M. SHELXS97, Program for Crystal Structure Solution. University of Göttingen: Germany 1997.
-
[33]
(33) Sheldrick, G. M. SHELXL97, Program for Crystal Structure Refinement. University of Göttingen: Germany 1997.
-
[34]
(34) Angamuthu, R.; Carroll, M. E.; Ramesh, M.; Rauchfuss, T. B. A new route to azadithiolato complexes. Eur. J. Inorg. Chem. 2011, 1029-1032.
-
[35]
(35) Xu, F.; Tard, C.; Wang, X.; Ibrahim, S. K.; Hughes, D. L.; Zhong, W.; Zeng, X.; Luo, Q.; Liu, X.; Pickett, C. J. Controlling carbon monoxide binding at di-iron units related to the iron-only hydrogenase sub-site. Chem. Commun. 2008, 606-608.
-
[36]
(36) Xiao, Z.; Xu, F.; Long, L.; Liu, Y.; Zampella, G.; De Gioia, L.; Zeng, X.; Luo, Q.; Liu, X. Influence of the basicity of internal bases in diiron model complexes on hydrides formation and their transformation into protonated diiron hexacarbonyl. J. Organomet. Chem. 2010, 695, 721-729.
-
[37]
(37) Wang, F. J.; Wang, M.; Liu, X. Y.; Jin, K.; Dong, W. B.; Li, G. H.; Akermark, B.; Sun, L. C. Spectroscopic and crystallographic evidence for the N-protonated (FeFeI)-Fe-I azadithiolate complex related to the active site of Fe-only hydrogenases. Chem. Commun. 2005, 3221-3223.
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