Skip to main content

Advertisement

SpringerLink
Log in

Modeling the active site of [FeFe]-hydrogenase: Electro-catalytic hydrogen evolution from acetic acid catalysed by [Fe 2 (μ-L)(CO) 6 ] and [Fe 2 (μ-L)(CO) 5 (PPh 3 )] (L=pyrazine-2,3-dithiolate, quinoxaline-2,3-dithiolate and pyrido[2,3-b]pyrazine-2,3-dithiolate)

  • Published:
Journal of Chemical Sciences Aims and scope Submit manuscript

Abstract

Compounds [Fe2{ μ-pydt}(CO)6] (pydt = pyrazine-2,3-dithiolate) (1), [Fe2{ μ-qdt}(CO)6] (qdt = quinoxaline-2,3-dithiolate) (2), [Fe2{ μ-ppdt}(CO)6] (ppdt = pyrido[2,3-b]pyrazine-2,3-dithiolate) (3), [Fe2 { μ-pydt}(CO)5PPh3] (4), [Fe2{ μ-qdt}(CO)5PPh3] (5) and [Fe2{ μ-ppdt}(CO)5PPh3] (6) have been synthesized in order to model the active sites of ‘[FeFe]-hydrogenase’. Compounds 1–6 have been characterized by routine spectral studies and unambiguously by single crystal X-ray crystallography. Supramolecular chemistry of compounds 1–6 have been described in terms of intermolecular interactions, observed in their respective crystal structures. Electro-catalytic hydrogen evaluation studies (from acetic acid) have been performed using compounds 1–6 as electro-catalysts. The mechanistic aspects of relevant electro–catalytic proton reductions have been discussed in detail.

In an attempt to model the active sites of [FeFe]-hydrogenase, a series of 1,2-enedithiolate-bridged di–iron complexes have been synthesized and structurally characterized. The electrochemical generation of di-hydrogen from an weak acid, mediated by these model complexes, has been demonstrated.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Scheme 2
Scheme 3
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Scheme 4
Figure 8
Scheme 5
Figure 9

Similar content being viewed by others

References

  1. Fontecilla-Camps J C, Volbeda A, Cavazza C and Nicolet Y 2007 Chem. Rev. 107 4273; Siegbahn P E M, Tye J W and Hall M B 2007 Chem. Rev. 107 4414; Vignais P M and Billoud B 2007 Chem. Rev. 107 4206; Adams M W W 1990 Biochim. Biophys. Acta 1020 115; Cammack R 1999Nature 397 214; Nicolet Y, Lemon B J, Fontecilla-Camps J C and Peters J W 2000 Trends Biochem. Sci. 25 138; Darensbourg M Y, Lyon E J, Zhao X and Georgakaki I P 2003 Proc. Natl. Acad. Sci. U.S.A. 1003683; Evans D J and Pickett C J 2003 Chem. Soc. Rev. 32 268; Alper J 2003 Science 299 1686; Song L C 2005 Acc. Chem. Res. 38 21; Adams M W W and Stiefel E I 1998 Science 282 1842; Vincent K A, Parkin A and Armstrong F A 2007 Chem. Rev. 107 4366; Frey M 2002 ChemBioChem. 3 153

  2. Nicolet Y, de Lacey A L, Vernede X, Fernandez V M, Hatchikian E C and Fontecilla-Camps J C 2001 J. Am. Chem. Soc. 1231596; Lemon B J and Peters J W 2000 J. Am. Chem. Soc. 122 3793; Lemon B J and Peters J W 1999 Biochemistry 38 12969; Nicolet Y, Piras C, Legrand P, Hatchikian E C and Fontecilla-Camps J C 1999 Structure 7 13; Bennett B, Lemon B J and Peters J W 2000 Biochemistry 39 7455; Peters, J W, Lanzilotta W N, Lemon B J and Seefeldt L C 1998 Science 282 1853

  3. Durgaprasad G, Bolligarla R and Das S K 2012 J. Organomet. Chem. 706 37; Durgaprasad G and Das S K 2012 J. Organomet. Chem. 717 29; Heinekey D M 2009 J. Organomet. Chem. 694 2671; Tard C and Pickett C J 2009 Chem. Rev. 109 2245; Capon J –F, Gloaguen F, Petillon F Y, Schollhammer P and Talarmin J 2009 Chem. Rev. 253 1476; Felton G A N, Mebi C A, Petro B J, Vannucci A K, Evans D H, Glass R S and Lichtenberger D L 2009 J. Organomet. Chem. 694 2681; Capon J –F, Gloaguen F, Petillon F Y, Schollhammer P and Talarmin J 2008 C. R. Chim. 11 842; Boyke A C, Rauchfuss T B, Wilson S R, Rohmer M -M and Benard M 2004 J. Am. Chem. Soc. 126 15151; Justice K A, Linck R C, Rauchfuss T B and Wilson S R 2004 J. Am. Chem. Soc. 126 13214; Gloaguen F, Lawrence J D and Rauchfuss T B 2001 J. Am. Chem. Soc. 123 9476; Gloaguen F, Lawrence J D, Rauchfuss T B and Rohmer M -M 2002 Inorg. Chem. 41 6573; Borg S J, Behrsing T, Best S P, Razavet M, Liu X and Pickett C J 2004 J. Am. Chem. Soc. 126 16988; Zhao X, Chiang C –Y, Miller M L, Rampersad M V and Darensbourg M Y 2003 J. Am. Chem. Soc. 125 518; Mejia-Rodriguez R, Chong D, Reibenspies J H, Soriaga M P and Darensbourg M Y 2004 J. Am. Chem. Soc. 12612004; Zhao X, Georgakaki I P, Miller M L, Mejia-Rodriguez R, Chiang C –Y and Darensbourg M Y 2002 Inorg. Chem. 41 3917; Cheah M H, Borg S J and Best S P 2007 Inorg. Chem. 46 1741; Borg S J, Tye J W, Hall M B and Best S P 2007 Inorg. Chem. 46 384; Ott S, Kritikos M, Akermark B and Sun L 2003 Angew. Chem. Int. Ed. 42 3285; Song L –C, Wang L –X, Tang M –Y, Li C –G, Song H –B and Hu Q –M 2009 Organometallics 28 3834; Song L –C, Tang M –Y, Mei S –Z, Huang J –H and Hu Q –M 2007 Organometallics 26 1575; Song L –C, Yang, Z Y, Hua Y J, Wang H T, Liu Y and Hu Q –M 2007 Organometallics 26 2106; Capon J –F, Gloaguen F, Schollhammer P and Talarmin J 2004 J. Electroanal. Chem. 566 241; Ott S, Kritikos M, Akermark B, Sun L and Lomoth R 2004 Angew. Chem. Int. Ed. 43 1006; Liu T, Wang M, Shi Z, Cui H, Dong W, Chen J, Akermark B and Sun L 2004 Chem.-Eur. J. 10 4474; Capon J –F, Gloaguen F, Schollhammer P and Talarmin J 2006 J. Electroanal. Chem. 595 47; Felton G A N, Vannucci A K, Okumura N, Lockett L T, Evans D H, Glass R S and Lichtenberger D L 2008 Organometallics 27 4671

  4. Durgaprasad G, Bolligarla R and Das S K 2011 J. Organomet.Chem. 696 3097

  5. Software for the CCD Detector System; Bruker Analytical X-Ray Systems, Inc.: Madison, WI, 1998

  6. Sheldrick G M, SADABS, Program for Absorption Correction with the Siemens SMART Area-Detector System; University of Göttingen: Göttingen, Germany, 1996

  7. Sheldrick G M, SHELXS-97, Program for Solution of Crystal Structures. University of Göttingen: Göttingen, Germany, 1997

  8. Sheldrick G M, SHELXL-97, Program for Refinement of Crystal Structures; University of Göttingen: Göttingen, Germany, 1997

  9. Zhao X, Georgakaki I P, Miller M L, Yarbrough J C and Darensbourg M Y 2001 J. Am. Chem. Soc. 123 9710

  10. Ott S, Borgstrom M, Kritikos M, Lomoth R, Bergquist J, Akermark B, Hammarstrom L and Sun L 2004 Inorg. Chem. 43 4683; Jiang S, Liu J, Shi Y, Wang Z, Akermark B and Sun L 2007 Dalton Trans. 896; Dong W, Wang M, Liu X, Jin K, Li G, Wang F and Sun L 2006 Chem. Commun. 305

  11. Felton G A N, Vannucci A K, Chen J, Lockett L T, Okumura N, Petro B J, Zakai U I, Evans D H, Glass R S and Lichtenberger D L 2007 J. Am. Chem. Soc. 129 12521

  12. Chong D, Georgakaki I P, Mejia-Rodriguez R, Sanabria-Chinchilla J, Soriaga M P and Darensbourg M Y 2003 Dalton Trans. 4158

  13. Duan L, Wang M, Li P, Na Y, Wang N and Sun L 2007 Dalton Trans. 1277

Download references

Acknowledgements

We thank CSIR, Government of India (project number 01(2556)/12/EMR-II) for financial support. The National X-ray Diffractometer facility at the University of Hyderabad by DST, Government of India, is gratefully acknowledged. We are grateful to UGC, New Delhi, for providing the infrastructure facility at University of Hyderabad under a UPE grant. GDP is grateful to CSIR, Government of India, New Delhi, for his fellowship. Special thanks are due to Dr. V. Madhu for initiating this project in our laboratory.

Author information

Authors and Affiliations

  1. School of Chemistry, University of Hyderabad, Hyderabad, 500 046, India

    GUMMADI DURGAPRASAD & SAMAR K DAS

Authors
  1. GUMMADI DURGAPRASAD
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. SAMAR K DAS
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to SAMAR K DAS.

Additional information

Supplementary information

The electronic supporting information can be seen at www.ias.ac.in/chemsci.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

DURGAPRASAD, G., DAS, S.K. Modeling the active site of [FeFe]-hydrogenase: Electro-catalytic hydrogen evolution from acetic acid catalysed by [Fe 2 (μ-L)(CO) 6 ] and [Fe 2 (μ-L)(CO) 5 (PPh 3 )] (L=pyrazine-2,3-dithiolate, quinoxaline-2,3-dithiolate and pyrido[2,3-b]pyrazine-2,3-dithiolate). J Chem Sci 127, 295–305 (2015). https://doi.org/10.1007/s12039-015-0774-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12039-015-0774-5

Keywords

Search

Navigation