Skip to main content

Structural Models for the FeMo-Cofactor and the P Clusters

  • Chapter
Catalysts for Nitrogen Fixation

Part of the book series: Nitrogen Fixation: Origins, Applications, and Research Progress ((NITR,volume 1))

  • 813 Accesses

Abstract

Nature uses unique heterometallic-sulfur assemblies, at the active sites of enzymes, to catalyze reactions of environmental and industrial importance. As an example, the bifunctional enzyme, carbon monoxide dehydrogenase/acetyl-CoA synthase (CODH/ACS), from Moorella thermoacetica catalyses the sequestration of carbon dioxide and its conversion to acetyl-CoA, which is a source of cell carbon, at moderate temperature and pressure. The process has similarities to the industrial Monsanto modification of the Reppe process, which produces acetic acid from carbon monoxide but uses relatively forcing conditions and expensive catalysts. At the active sites of this enzyme are unusual nickel-iron-sulfur assemblies (Figure 1 ; Doukov et al., 2002). The enzyme nitrogenase catalyses the even more important conversion of dinitrogen to ammonia and again nature utilizes complex and specialized metal-sulfur clusters. In molybdenum nitrogenase, the reduction of dinitrogen occurs at the iron-molybdenum-cofactor (FeMo-cofactor). In addition, within the protein are unusual iron-sulfur clusters, which are probably involved in electron transfer, called the P cluster. The structures of both the FeMo-cofactor and the P cluster were described in Chapter 4.

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

Access this chapter

Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 129.00
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 169.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 169.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  • Al-Ahmad, S. A., Kampf, J. W., Dunham, R. W., and Coucouvanis, D. (1991). Oxidation by elemental sulfur and coupling of Fe/S complexes — synthesis and structural characterization of (Et4N)4[Fe4S6(SEt)4], a new Fe/S cluster with a linear Fe4 backbone. Inorg. Chem., 30, 1163–1164.

    Article  CAS  Google Scholar 

  • Barclay, J. E., Diaz, M. L., Evans, D. J., Garcia, G., Santana, M. D., and Torralba, M. C. (1997a). The binding of amino acids to the differentiated iron in 3:1 site-differentiated {Fe4S4} clusters. Inorg. Chim. Acta, 258, 211–219.

    Article  CAS  Google Scholar 

  • Barclay, J. E., Evans, D. J., Garcia, G., Perez, J. M., Santana, M. D., and Torralba, M. C. (1997b). Bridged site-differentiated [Fe4S4]2+ double cubanes: Synthesis and characterization. An. Quim. Int. Ed., 93, 17–21.

    CAS  Google Scholar 

  • Barclay, J. E., Evans, D. J., Garcia, G., Santana, M. D., Torralba, M. C, and Yago, J. M. (1995). Binding of the {MoFe3S4}3+ core by a tridentate thiolate and chemical analogues of the molybdenum co-ordination environment in the iron-molybdenum cofactor of nitrogenase. J. Chem. Soc, Dalton Trans., 1965–1971.

    Google Scholar 

  • Barclay, J. E., Evans, D. J., and Longhurst, S. (1996). Spectroscopic evidence for a bis(sulfido-bridged) dimeric Fe4S4 cluster — a step toward a synthetic analogue of the P cluster of nitrogenase. An. Quim. Int. Ed, 92, 381–384.

    CAS  Google Scholar 

  • Bose, K. S., Sinn, E., and Averill, B. A. (1984). Synthesis and X-ray structure of the [Fe4S4(CO)12]2 ion — an example of intermolecular disulfide formation by the (µ-S)2Fe2(CO)6 unit. Organometallies,3, 1126–1128.

    Article  CAS  Google Scholar 

  • Cen, W., MacDonnell, F. M., Scott, M. J., and Holm R. H. (1994). Heterometal clusters containing the cuboidal Fe4S4 fragment — synthesis, electron-distribution, and reactions. Inorg. Chem., 33, 5809–5818.

    Article  CAS  Google Scholar 

  • Challen, P. R., Koo, S-M., Kim, C. G., Dunham, W. R., and Coucouvanis, D. (1990a). Nitrogenase substrates as intercluster bridging units between the Mo atoms in doubly bridged, double cubanes. The synthesis and characterization of the [[MoFe3S4Cl2(Cl4cat)]2(µ2-S)(µ2-L)]n- (L = N2H4, n = 4; L = CN-, n = 5). J.Amer. Chem. Soc., 112, 8606–8607.

    Article  CAS  Google Scholar 

  • Challen, P. R., Koo, S-M., Dunham, W. R., and Coucouvanis, D. (1990b). New U2-S2-coupled, singly bridged double cubane with the [(Fe4S4Cl3)2S]4- core — the stepwise synthesis and structural characterization of (η-Bu4N)2(Ph4P)2[(Fe4S4Cl3)2S]. J. Amer. Chem. Soc,112, 2455–2456.

    Article  CAS  Google Scholar 

  • Christou, G., Sabat, M., Ibers, J. A., and Holm, R. H. (1982). A new structural type in iron-sulfidethiolate chemistry: preparation, properties and structure of the hexanuclear cluster [Fe6S9(S-t-C4H9)2]4-. Inorg. Chem., 21, 3518–3526.

    Article  CAS  Google Scholar 

  • Chu, C. T-W., and Dahl, L. F. (1977). Structural characterization of [AsPh4]+[Fe4(NO)7(µ3-S)3]-. Stereochemical and bonding relationship of the Roussin black monoanion with the red ethyl ester, Fe2(NO)4(µ2-SC2H5)2, and Fe4(NO)4(µ3-S)4. Inorg. Chem., 16, 3245–3251.

    Article  CAS  Google Scholar 

  • Coucouvanis, D. (1991). Use of preassembled Fe/S and Fe/Mo/S clusters in the stepwise synthesis of potential analogs for the Fe/Mo/S site in nitrogenase. Acc. Chem. Res., 24, 1–8.

    Article  CAS  Google Scholar 

  • Coucouvanis, D, Demadis, K. D., Malinak, S. M., Mosier, P.E., Tyson, M. A., and Laughlin, L. J. (1996). Catalytic and stoichiometric multielectron reduction of hydrazine to ammonia and acetylene to ethylene with clusters that contain the MFe3S4 cores (M = Mo,V). Relevance to the function of nitrogenase. J. Mol. Cat. A: Chem., 107, 123–135.

    Article  CAS  Google Scholar 

  • Coucouvanis, D., Han, J. H., and Moon, N. (2002). Synthesis and characterization of sulfur-voided cubanes. Structural analogues for the MoFe3S3 subunit in the nitrogenase cofactor. J.Amer. Chem. Soc., 124, 216–224.

    Article  CAS  Google Scholar 

  • D’Addario, S., Demartin, F., Grossi, L., Lapalucci, M. C, Laschi, F., Longoni, G., and Zanello, P. (1993). Redox behavior of the black Roussinate [Fe4S3(NO)7] monoanion. Synthesis and spectroscopic characterization of the [Fe4S3(NO)7]n- (n = 2, 3) anions and crystal structures of the mono- and dianions in their [NEt4]+ salts. Inorg. Chem., 32, 1153–1160.

    Article  Google Scholar 

  • Dance, I. (2003). The consequences of an interstitial N atom in the FeMo cofactor of nitrogenase. Chem. Commun., 324–325.

    Google Scholar 

  • Demadis, K. D., Campana, C. F., and Coucouvanis, D. (1995). Synthesis and structural characterization of the new Mo2Fe6S8(PR3)6(Cl-4-cat)2 clusters — double cubanes containing 2 edge-linked [MoFe3S4]2+ reduced cores. J. Amer. Chem. Soc, 117, 7832–7833.

    Article  CAS  Google Scholar 

  • Demadis, K. D., and Coucouvanis, D. (1995a). Synthesis, structural characterization, and properties of new single and double cubanes containing the MoFe3S4 structural unit and molybdenum-bound polycarboxylate ligands — clusters with a molybdenum-coordination environment similar to that in the iron molybdenum cofactor of nitrogenase. Inorg. Chem., 34, 436–448.

    Article  CAS  Google Scholar 

  • Demadis, K. D., and Coucouvanis, D. (1995b). Structural characterization and reactivity properties of a new class of Mo/Fe/S double cubanes with Mo-bound S-µ2-η1, O-η1 mercapto carboxylate ligands. New catalysts for the reduction of hydrazine to ammonia and implications regarding the function of nitrogenase. Inorg. Chem., 34, 3658–3666.

    Article  CAS  Google Scholar 

  • Demadis, K. D., Malinak, S. M, and Coucouvanis, D. (1996). Catalytic reduction of hydrazine to ammonia with MoFe3S4-polycarboxylate clusters. Possible relevance regarding the function of the molybdenum-coordinated homocitrate in nitrogenase. Inorg. Chem., 35, 4038–4046.

    Article  CAS  Google Scholar 

  • Doukov, T. I., Iverson, T. M., Seravalli, J., Ragsdale, S. W., and Drennan, C. L. (2002). A Ni-Fe-Cu center in a bifunctional carbon monoxide dehydrogenase/acetyl-CoA synthase. Science, 298, 567–572.

    Article  CAS  Google Scholar 

  • Einsle, O., Tezcan, F. A., Andrade, S. L. A., Schmid, B., Yoshida, M., Howard, J. B., and Rees, D. C. (2002). Nitrogenase MoFe-protein at 1.16 Ã… resolution: A central ligand in the FeMo-cofactor. Science, 297, 1696–1700.

    Article  CAS  Google Scholar 

  • Evans, D. J., Hughes, D. L., and Silver, J. (1997). Low-coordinate homoleptic iron(11) thiolates revisited. Inorg. Chem., 36, 741–148.

    Article  Google Scholar 

  • Evans, D. J., Hill, M. S., and Hitchcock, P. B. (2003). Tuning low-coordinate metal environments: High spin d5-d7 complexes supported by bis(phosphinimino)methyl ligation. J. Chem. Soc., Dalton Trans., 570–574.

    Google Scholar 

  • Fjare, D. E., and Gladfelter, W. L. (1981). Synthesis and reactivity of an anionic tetrairon nitride cluster. Crystal and molecular structure of PPN[Fe4N(CO)12]. Inorg. Chem., 20, 3533–3539.

    Article  CAS  Google Scholar 

  • Glidewell, C, Lambert, R. J., Harman, M. E., and Hursthouse, M. B. (1990). Reactions of nucleophiles with bis(µ-thiosulfato-S)-bis(dinitrosylferrate)(2-), [Fe2(S2O3)2(NO)4]2- , and of electrophiles with heptanitrosyltri-µ3-thio-tetraferrate(1-), [Fe4S3(NO)7]- — new routes to bis(µ-organothiolato)-bis(dinitrosyliron) complexes [Fe2(SR)2(NO)4] and the crystal and molecular-structure of trimethylsulfonium heptanitrosyltri-µ3-thio-tetraferrate(1-), SMe3[Fe4S3(NO)7]. J. Chem. Soc., Dalton Trans., 2685–2690.

    Google Scholar 

  • Goh, C, Segal, B. M., Huang, J., Long, J. R., and Holm, R. H. (1996). Polycubane clusters: Synthesis of [Fe4S4PR3)](1+0) ) (R=But,Cy,Pri) and [Fe4S4]0 core aggregation upon loss of phosphine. J. Amer. Chem. Soc., 715, 11844–11853.

    Article  Google Scholar 

  • Goh, C. and Holm, R. H. (1998). Synthesis and structures of the cuboidal iron-sulfur-nitrosyl-phosphine clusters [Fe4S3(NO)4(PR3)3]0,1+ (R = Et, Pri, C6H11). Inorg. Chim. Acta, 270, 46–54.

    Article  CAS  Google Scholar 

  • Goh, C, Nivorozhkin, A., Yoo, S. J., Bominaar, E. L., Münck, E., and Holm, R. H. (1998). The mixed-valence double-cubanoid cluster [Fe8Si2(Bu’NC)12]: Synthesis, structure, and exchange coupling of a new structural array of four Fe(III) sites. Inorg. Chem., 37, 2926–2932.

    Article  CAS  Google Scholar 

  • Han, J. H., Beck, K., Ockwig, N., and Coucouvanis, D. (1999). Synthetic analogues for the MoFe3S3 subunit of the nitrogenase cofactor: structural features associated with the total number of valence electrons and the possible role of M-M and multiple M-S bonding in the function of nitrogenase. J. Amer. Chem. Soc., 121, 10448–10449.

    Article  CAS  Google Scholar 

  • Han, J., and Coucouvanis, D. (2001). A new function of the (µ3-S) ligand in an Fe4S4 cluster: synthesis and structure of the high-nuclearity Mo/Fe/S cluster, Fe(DMF)Cl(Cl4-cat)2Mo2Fe2S4(PEt3)2ClFe4S4(PEt3)3(CO)6Cl. J. Amer. Chem. Soc.,123, 11304–11305.

    Article  CAS  Google Scholar 

  • Han, J., Koutmos, M., Al-Ahmad, S., and Coucouvanis, D. (2001). Rational synthesis of high nuclearity Mo/Fe/S clusters: reductive coupling approach in convenient synthesis of (Cl4-cat)2Mo2Fe6S8(PR3)6[R = Et, nPr, nBu] and new [(Cl4-cat)2Mo2Fe2S3O(PEt3)3CM·1/2(Fe(PEt3)2(MeCN)4) and (Cl4-cat)2Mo2Fe3S5(PEt3)5 clusters. Inorg. Chem., 40, 5985–5999.

    Article  CAS  Google Scholar 

  • Hinnemann, B., and Nørskov, J. K. (2003). Modeling a central ligand in the nitrogenase FeMo cofactor. J. Amer. Chem. Soc., 125, 1466–1467.

    Article  CAS  Google Scholar 

  • Holm, R. H. (1992). Trinuclear cuboidal and heterometallic cubane-type iron-sulfur clusters: New structural and reactivity themes in chemistry and biology. Adv. Inorg. Chem., 38, 1–71.

    Article  CAS  Google Scholar 

  • Huang, J., and Holm, R. H. (1998). Synthesis, identification, and reactivity properties of symmetrical MoFe3S4 double cubanes with Fe-S-Fe and Fe-O-Fe bridges. Inorg. Chem., 37, 2247–2254.

    Article  CAS  Google Scholar 

  • Huang, J., Mukerjee, S., Segal, B. M., Akashi, H., Zhou, J., and Holm, R. H. (1997). Molybdenum-iron sulfide-bridged double cubanes. J. Amer. Chem. Soc., 119, 8662–8674.

    Article  CAS  Google Scholar 

  • Hauser, C, Bill E., and Holm, R. H. (2002). Single- and double-cubane clusters in the multiple oxidation states [VFe3S4] (3+, 2+, 1+). Inorg. Chem., 41, 1615–1624.

    Article  CAS  Google Scholar 

  • Kim, J. S., and Rees, D.C. (1992). Structural models for the metal centers in the nitrogenase molybdenum-iron protein. Science, 257, 1677–1682.

    Article  CAS  Google Scholar 

  • Laughlin, L. J., and Coucouvanis, D. (1995). Use of [MoFe3S4]3+ single cubanes in the catalytic reduction of acetylene to ethylene and ethane. Identification of molybdenum and iron atoms as catalytic sites during substrate reductions and implications for nitrogenase action. J. Amer. Chem. Soc, 117, 3118–3125.

    Article  CAS  Google Scholar 

  • MacDonnell, F. M., Ruhlandt-Senge, K., Ellison, J. J., Holm, R. H., and Power, P. P. (1995). Sterically encumbered iron(II) thiolate complexes: Synthesis and structure of trigonal planar [Fe(SR)3]- (R = 2,4,6-t-Bu3C6H2) and Mössbauer spectra of two- and three-coordinate complexes. Inorg. Chem., 34, 1815–1822.

    Article  CAS  Google Scholar 

  • Malinak, S. M., Simeonov, A. M., Mosier, P. E., McKenna, C. E. and Coucouvanis, D. (1997) Catalytic reduction of cis-dimethyldiazene by the [MoFe3S4]3+ clusters. The four-electron reduction of a N=N bond by a nitrogenase-relevant cluster and implications for the function of nitrogenase. J. Amer. Chem. Soc, 119, 1662–1667.

    Article  CAS  Google Scholar 

  • Mascharak, P. K., Armstrong, W. H., Mizobe, Y., and Holm, R. H. (1983). Single cubane-type MFe3S4 clusters (M = Mo, W): Synthesis and properties of oxidized and reduced forms and the structure of (Et4N)3[MoFe3S4(S-p-C6H4Cl)4(3,6-(C3H5)2C6H2O2)]. J. Amer. Chem. Soc., 105, 475–483.

    Article  CAS  Google Scholar 

  • Mayer, S. M., Lawson, D. M., Gormal, C. A., Roe, M. S., and Smith, B. E. (1999). New insights into structure-function relationships in nitrogenase: A 1.6 Ã… resolution X-ray crystallographic study of Klebsiella pneumoniae MoFe-protein. J. Mol. Biol., 292, 871–891.

    Article  CAS  Google Scholar 

  • Mosier, P. E., Kim, C. G., and Coucouvanis, D. (1993). Synthesis, structural characterization, and properties of singly bridged double cubanes containing two [(Cl4-cat)MoFe3S4Cl3]2- subunits and hydrazine or pyrazine bridges. Inorg. Chem., 32, 2620–2621.

    Article  CAS  Google Scholar 

  • Nordlander, E., Lee, S.C., Cen, W., Wu, Z. Y., Natolu, A. D., Cicco, A., Filipponi, A., Hedman, B., Hodgson, K.O., and Holm, R. H. (1993). Heterometal cuboidal clusters MFe4S6(PEt3)4Cl (M = V, Mo) — synthesis, structural-analysis by crystallography and EXAFS, and relevance to the core structure of the iron molybdenum cofactor of nitrogenase. J. Amer. Chem. Soc, 115, 5549–5558.

    Article  CAS  Google Scholar 

  • Osterloh, F., Achim, C, and Holm, R. H. (2001). Reduced molybdenum-iron-sulfur clusters of nuclearities eight and sixteen including a topological analogue of the P-cluster of nitrogenase. Inorg. Chem., 40, 224–232.

    Article  CAS  Google Scholar 

  • Osterloh, F., Sanakis, Y., Staples, R. J., Münck, E., and Holm, R. H. (1999). Molybdenum-iron-sulfur cluster containing structural elements relevant to the P-cluster of nitrogenase. Angew. Chem., Int. Ed. Engl., 38, 2066–2070.

    Article  CAS  Google Scholar 

  • Palermo, R. E., Singh, R., Bashkin, J. K., and Holm, R. H. (1984). Molybdenum atom ligand substitution reactions of MoFe3S4 cubane-type clusters: synthesis and structures of clusters containing Mo-bound pseudosubstrates of nitrogenase. J. Amer. Chem. Soc., 106, 2600–2612.

    Article  CAS  Google Scholar 

  • Pergola, R. D., Bandini, C, Demartin, F., Diana, E., Garlaschelli, L., Stanghellini, P. L., and Zanello, P. (1996). Characterization, redox properties and structures of the iron nitridocarbonyl clusters [Fe4N(CO)11{PPh(C5H4FeC5H5)2}]-, [Fe6N(CO),5]3- and [Fe6H(N)(CO)15]2-. J. Chem. Soc, Dalton Trans., 141–154.

    Google Scholar 

  • Pergola, R. D., Garlaschelli, L., Manassero, M., Sansoni, M., Strumolo, D., Fabrizi de Biani, F., and Zanello, P. (2001). Reactivity of nitrido-carbonyl clusters: Synthesis and solid state structure of [Fe5MnN(CO)16]2- and [Fe6N(CO)14NO]2-; oxidation of a cluster-coordinated nitride. J. Chem. Soc., Dalton Trans., 2179–2183.

    Google Scholar 

  • Peters, J. W., Stowell, M. H. B., Soltis, S. M., Finnegan, M. G., Johnson, M. K., and Rees, D. C. (1997) Redox-dependent structural changes in the nitrogenase P-cluster. Biochemistry, 1181–1187.

    Google Scholar 

  • Power P. P., and Shoner, S. C. (1991). The neutral transition metal thiolates [M(SAr)2]2- (M = Mn, Fe or Co, Ar = 2,4,6-t-Bu3C6H2). Angew. Chem., Int. Ed. Engl., 30, 330–332.

    Article  Google Scholar 

  • Ruhlandt-Senge, K., and Power, P. P. (1992). The synthesis and characterization of metal derivatives of the new, conveniently prepared, bulky thiolato ligand HSC6H2-2,4,6-Ph3. Bull. Soc. Chim. Fr., 129, 594–598.

    Google Scholar 

  • Scott, M. J., and Holm, R. H. (1993). Tetranuclear cuboidal and hexanuclear prismatic iron-sulfur-nitrosyl clusters. Angew. Chem., Int. Ed. Engl, 32, 564–566.

    Article  Google Scholar 

  • Stack, T. D. P., Carney, M. J., and Holm, R. H. (1989). Formation of bridged [Fe4S4]2+ double cubanes by site-specific reactions: Electron-transfer coupling across sulfur containing bridges of variable length. J. Amer. Chem. Soc., 111, 1670–1676.

    Article  CAS  Google Scholar 

  • Strasdeit, H., Krebs, B., and Henkel, G. (1984). Synthetic routes to [Fe6S9(SR)2]4- clusters (R = alkyl). Their spectroscopic and magnetic properties and the solid-state structure of [Fe6S9SCH2Ph2]4- and [(Fe6S9(SMe)2)2Na2]6-. Inorg. Chem., 23, 1816–1825.

    Article  CAS  Google Scholar 

  • Tachikawa, M., Stein, J., Muetterties, E. L., Teller, R. G., Beno, M. A., Gebert, E., and Williams, J. M. (1980). Metal clusters with exposed and low-coordinate nitride nitrogen atoms. J. Amer. Chem. Soc., 102, 6648–6649.

    Article  CAS  Google Scholar 

  • Zhang, Y., Zuo, J.-L., Zhou, H.-C, and Holm, R. H. (2002). Rearrangement of symmetrical dicubane clusters into topological analogues of the P cluster of nitrogenase: Nature’s choice? J.Amer. Chem. Soc., 124, 14292–14293.

    Article  CAS  Google Scholar 

  • Zhou, H.-C, and Holm, R. H. (2003). Synthesis and reactions of cubane-type iron-sulfur-phosphine clusters, including soluble clusters of nuclearities 8 and 16. Inorg. Chem., 42, 11–21.

    Article  CAS  Google Scholar 

  • Zhou, H. C, Su, W. P., Achim, C, Rao, V. P., and Holm, R. H. (2002). High-nuclearity sulfide-rich molybdenum-iron-sulfur clusters: reevaluation and extension. Inorg. Chem., 41, 3191–3201.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Editor information

Editors and Affiliations

Rights and permissions

Reprints and permissions

Copyright information

© 2004 Springer Science+Business Media Dordrecht

About this chapter

Cite this chapter

Evans, D.J. (2004). Structural Models for the FeMo-Cofactor and the P Clusters. In: Smith, B.E., Richards, R.L., Newton, W.E. (eds) Catalysts for Nitrogen Fixation. Nitrogen Fixation: Origins, Applications, and Research Progress, vol 1. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-3611-8_8

Download citation

  • DOI: https://doi.org/10.1007/978-1-4020-3611-8_8

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-90-481-6675-6

  • Online ISBN: 978-1-4020-3611-8

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics