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Iron-Molybdenum-Sulfur Clusters

  • C. David Garner
  • Stephen R. Acott
  • George Christou
  • David Collison
  • Frank E. Mabbs
  • Vasili Petrouleas
  • Christopher J. Pickett

Abstract

The recognition that molybdenum is present in the nitrogenase enzymes as an extraetable cofactor, containing iron, molybdenum, and sulfur in the approximate ratios 7:1:6,1-4 stimulated much interest in the synthesis and study of compounds containing these three elements. This article describes those compounds presently known to contain an Fe-Mo-S framework; their physical properties are then compared with those of the iron-molybdenum cofactor, with particular emphasis being given to systems containing Fe3MoS4 cubane-like clusters.

Keywords

Iron Atom Cluster Complex Electrochemical Reversibility Clostridium Pasteurianum Ligand Substitution Reaction 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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References

  1. 1.
    V. K. Shah and W. J. Brill, Isolation of an Iron-Molybdenum Cofactor from Nitrogenase, Proc. Natl. Acad. Sci. USA 74:3249 (1977).PubMedCrossRefGoogle Scholar
  2. 2.
    B. E. Smith, Studies on the Iron-Molybdenum Cofactor from the Nitrogenase Molybdenum-Iron Protein of Klebsiella pneumoniae in: “Molybdenum Chemistry of Biological Significance,” W. E. Newton and S. Otsuka, eds., Plenum Press, New York, p. 179 (1979)Google Scholar
  3. 3.
    B. K. Burgess, D. B. Jacobs, and E. I. Stiefel, Large-Scale Purification of High Activity Azotobacter vinelandii Nitrogenase, Biochim. Biophys. Acta 614:196 (1980).PubMedGoogle Scholar
  4. 4.
    B. K. Burgess, E. I. Stiefel, and W. E. Newton, Oxidation-Reduction Properties and Complexation Reactions of the Iron-Molybdenum Cofactor of Nitrogenase, J. Biol. Chem. 255:353 (1980).PubMedGoogle Scholar
  5. 5.
    D. Coucouvanis, N. C. Baenziger, E. D. Simhon, P. Stremple, D. Swenson, A. Kostikas, A. Simopoulos, V. Petrouleas, and V. Papaefthmiou, Heterodinuclear Di-y-sulfido Bridged Dimers Containing Iron and Molybdenum or Tungsten. Structures of (Ph4P)2(FeMS9) Complexes (M = Mo, W), J. Am. Chem. Soc. 102:1730 (1980).CrossRefGoogle Scholar
  6. 6.
    R. H. Tieckelmann and B. A. Averill, Preparation and Properties of the Bis(phenylmercapto)iron(III)-di-y-sulfidoiron(II)-di-μ-sulfidomolybdate(VI) Ion, [(PhS)2FeS2FeS2MoS2]3-, Inorg. Chim. Acta 46:L35 (1980).CrossRefGoogle Scholar
  7. 7.
    A. Müller and S. Sarkar, Thioheteroanions — Unusual Metal-Ligand Interactions and Reactions, Angew. Chem. Int. Ed. Engl. 16:705 (1977).CrossRefGoogle Scholar
  8. 8.
    D. Coucouvanis, E. D. Simhon, D. Swenson, and N. C. Baenziger, X-Ray Crystal Structure of Bis(tetraethylammonium) Di-μ-thio-bis(phenylthio)ferrate(III)-dithiomolybdate(V), [Et4N]2[(PhS)2FeMbS4] : A Dinuclear Complex with the FeS2Mo Core, J. Chem. Soc., Chem. Coram. 316 (1979).Google Scholar
  9. 9.
    R. H. Tieckelmann, H. C. Silvis, T. A. Kent, B. H. Huynh, J. V. Waszczak, B.- K. Teo, and B. A. Averill, Synthetic Moly-bdenum-Iron-Sulfur Clusters. Preparation, Structures, and Properties of the [S2MoS2Fe(SC6H5)2]2- and [S2MoS2FeCl2]2-Ions, J. Am. Chem. Soc. 102:5550 (1980).CrossRefGoogle Scholar
  10. 10.
    A. Müller, H. Bögge, H.- G. Tölle, R. Jostes, U. Schimanski and M. Dartmann, MoS4 2- and MoOS3 2- as Structurally Versatile and Biochemically Interesting Ligands in Crystalline Multinuclear Cu- and Fe- Complexes, Angew. Chem. Int. Ed. Engl, 19:654 (1980).CrossRefGoogle Scholar
  11. 11.
    J. W. McDonald, G. D. Friesen and W. E. Newton, Synthesis and Characterization of [Et4N]3[Fe(MbS4)2]. A New Fe-Mo-S Complex, Inorg. Chim, Acta 46:L79 (1980);CrossRefGoogle Scholar
  12. 11a.
    D. Coucouvanis, E. D. Simhon, N. C. Baenziger, Successful Isolation of a Reduced Tetrathiometallate Complex. Synthesis and Structural Characterization of the [(MoS4)2Fe]3- Trianion, J. Am. Chem. Soc. 102:6644 (1980).CrossRefGoogle Scholar
  13. 12.
    D. Coucouvanis, N. C. Baenziger, E. D. Simhon, P. Stremple, D. Swenson, A. Simopoulos, A. Kostikas, V. Petrouleas, and V. Papaefthymiou, Synthesis and Structural Characterization of the (Ph4P)2[Cl2FeS2MS2FeCl2] Complexes (M = Mo, W). First Example of a Doubly Bridging MoS4 Unit and its Possible Relevance as a Structural Feature in the Nitrogenase Active Site, J. Am. Chem. Soc. 102:1732 (1980).CrossRefGoogle Scholar
  14. 13.
    H. C. Silvis, R. H. Tieckelmann, and B. A. Averill, Preparation and Properties of the Tetrakis[tetrathiomolybdato(VI)-μ3-sulfidoiron] Cluster, [Fe4Mo4S20]6-, Inorg. Chim. Acta 36:1423 (1979).CrossRefGoogle Scholar
  15. 14.
    S. R. Acott, C. D. Garner, and T. J. King, unpublished results.Google Scholar
  16. 15.
    G. Christou and C. D. Garner, Synthesis and Proton Magnetic Resonance Properties of Fe3MS4 (M = Mo or W) Cubane-like Cluster Dimers, J. Chem. Soc. (Dalton), 2354 (1980).Google Scholar
  17. 16.
    T. E. Wolff, J. M. Berg, K. O. Hodgson, R. B. Frankel, and R. H. Holm, Synthetic Approaches to the Molybdenum Site in Nitrogenase. Preparation and Structural Properties of the Molybdenum-Iron-Sulfur “Double-Cubane” Cluster Complexes [Mo2Fe6S8(SC2H5)9]3- and [Mo2Fe6S9(SC2H5)8]3-, J. Am. Chem. Soc. 101:4140 (1979).CrossRefGoogle Scholar
  18. 17.
    T. E. Wolff, P. P. Power, R. B. Frankel, and R. H. Holm, Synthesis and Electronic and Redox Properties of “Double-Cubane” Cluster Complexes Containing MoFe3S4 and WFe3S4 Cores, J. Am. Chem. Soc. 102:4694 (1980).CrossRefGoogle Scholar
  19. 18.
    G. Christou, C. D. Garner, F. E. Mabbs and T. J. King, Crystal Structure of Tris(tetra-n-butylammonium) Tri-u-benzenethio-lato-bis{tri-}-sulfido-[μ3-sulfido-tris(benzenethiolatoiron) iron)]molybdenum, [Bu4N]3[{(PhSFe)3MoS4}2(SPh)3]; an Fe3MoS4 Cubic Cluster Dimer, J. Chem. Soc., Chem. Comm. 740 (1978).Google Scholar
  20. 19.
    G. Christou, C. D. Garner, F. E. Mabbs and M. G. B. Drew, Thiol Exchange Reactions of Iron-Molybdenum-Sulfur Clusters; Preparation and X-Ray Crystal Structure of [Et4N]3[Fe6Mo2S8 (SCH2CH2OH)9], a Water Soluble Iron-Molybdenum-Sulfur Cluster, J. Chem. Soc., Chem. Comm. 91 (1979).Google Scholar
  21. 20.
    S. R. Acott, G. Christou, C. D. Garner, T. J. King, F. E. Mabbs and R. M. Miller, Isolation and Crystal Structure of [Et4N]3[Fe6Mo2S8(SEt)9], Inorg. Chim. Acta 35:L337 (1979).CrossRefGoogle Scholar
  22. 21.
    G. Christou, C. D. Garner, T. J. King, C. E. Johnson, and J. D. Rush, Isolation and Characterization by X-Ray Crystallography and Mössbauer Measurements of [NEt4]3[Fe6W2S8(SPh)6 (OMe)3], and Iron-Tungsten-Cubic Cluster Dimer, J. C. S., Chem. Comm., 503 (1979).Google Scholar
  23. 22.
    C. D. Garner, S. R. Acott, G. Christou, D. Collison, F. E. Mabbs and R. M. Miller, Studies of Iron-Molybdenum-Sulfur Clusters, in: “Current Perspectives in Nitrogen Fixation,” A. H. Gibson and W. E. Newton, eds., Australian Academy of Science, Canberra, p. 40 (1981); G. Christou, C. D. Garner and T. J. King, unpublished results.Google Scholar
  24. 23.
    T. E. Wolff, J. M. Berg, C. Warrick, K. O. Hodgson, R. H. Holm and R. B. Frankel, The Molybdenum-Iron-Sulfur Cluster Complex [Mp2Fe6S9(SC2H5)8]3-. A Synthetic Approach to the Molybdenum Site in Nitrogenase, J. Am. Chenu Soc. 100:4630 (1978).CrossRefGoogle Scholar
  25. 24.
    T. E. Wolff, J. M. Berg, P. P. Power, K. O. Hodgson and R. H. Holm, Structural Characterization of the Iron-Bridged “Double Cubane” Cluster Complexes [Mo2Fe7S8(SC2H5)12]3-and [M2Fe7S8(SCH2C6H5)12]4- (M = Mo, W) Containing MFe3S4 Cores, Inorg. Chem. 19:430 (1980).CrossRefGoogle Scholar
  26. 25.
    T. E. Wolff, J. M. Berg, and R. H. Holm, Synthesis, Structure and Properties of the Cluster Complex [MoFe4S4(SC2H5)3 (C6H4O2)3]3-, Containing a Single Cubane-Type MoFe3S4 Core, Inorg. Chem. 20:174 (1981).CrossRefGoogle Scholar
  27. 26.
    G. Christou and C. D. Garner, Ligand Substitution Reactions of Iron-Molybdenum-Sulfur Cubane-like Cluster Dimers; Selective Halide Incorporation, J. Chem. Soc., Chem. Comm. 613 (1980)Google Scholar
  28. 27.
    Further investigations to those described in Ref. 19 have shown that this thiolate exchange proceeds only at the iron atoms.Google Scholar
  29. 28.
    L. Que Jr., M. A. Bobrik, J. A. Ibers, and R. H. Holm, Synthetic Analogs of the Active Sites of the Iron-Sulfur Proteins. VII. Ligand Substitution Reactions of the Tetranuclear Clusters [Fe4S4(SR)4]2- and the Structure of [(CH3)4N]2[Fe4S4(SC6H5)4], J. Am. Chem. Soc. 96:4168 (1974).PubMedCrossRefGoogle Scholar
  30. 29.
    G. B. Wong, M. A. Bobrik, and R. H. Holm, Inorganic Derivatives of Iron Sulfide Thiolate Dimers and Tetramers: Synthesis and Properties of the Halide Series [Fe2S2X4]2- and [Fe4S4X4]2- (X = Cl, Br, I), Inorg. Chem. 17:578 (1978).CrossRefGoogle Scholar
  31. 30.
    J. R. Benemann, G. M. Smith, P. J. Kostel, and C. E. McKenna, Tungsten Incorporation into Azotobacter vinelandii Nitrogenase, FEBS Lett. 29:219 (1973).PubMedCrossRefGoogle Scholar
  32. 31.
    H. H. Nagatani and W. J. Brill, Nitrogenase Vanadium. Effect of Molybdenum, Tungsten, and Vanadiun on the Synthesis of Nitrogenase Compounds in Azotobacter vinelandii, Biochim. Biophys. Acta 362:160 (1974).PubMedCrossRefGoogle Scholar
  33. 32.
    G. Christou, C. D. Garner, R. M. Miller and T. J. King, Preparation and Crystal Structure of [NEt4]3[Fe6W2S8(SEt)9]; Structural and Electrochemical Comparisons with its Molybdenum Analogue, J. Inorg. Biochem. 11:349 (1979).CrossRefGoogle Scholar
  34. 33.
    R. D. Shannon and C. T. Prewitt, Effective Ionic Radii in Oxides and Fluorides, Acta Cryst. B25:925 (1969).Google Scholar
  35. 34.
    S. P. Cramer, K. O. Hodgson, W. O. Gillum and L. E. Mortenson, The Molybdenum Site of Nitrognease. Preliminary Structural Evidence from X-Ray Absorption Spectroscopy, J. Am. Chem. Soc. 100:3398 (1978).CrossRefGoogle Scholar
  36. 35.
    S. P. Cramer, W. O. Gillum, K. O. Hodgson, L. E. Mortenson, E. I. Stiefel, J. R. Chisnel, J. W. J. Brill, and V. K. Shah, The Molybdenum Site of Nitrogenase. 2. A Comparative Study of Mo-Fe Proteins with the Iron-Molybdenum Cofactor by X-Ray Absorption Spectroscopy, J. Am. Chem. Soc. 100:3814 (1978).CrossRefGoogle Scholar
  37. 36.
    B. K. Burgess, S.- S. Yang, C. B. You, J.- G. Li, G. D. Friesen, W.- H. Pan, E. I. Stiefel, W. E. Newton, S. D. Conradson, and K. O. Hodgson, Iron-Molybdenum Cofactor and its Complementary Protein from Azotobacter vinelandii UW 45 in: “Current Perspectives in Nitrogen Fixation,” A. H. Gibson and W. E. Newton, eds., Australian Academy of Science, Canberra, p. 71 (1981).Google Scholar
  38. 37.
    G. Christou, C. D. Garner, R. M. Miller, C. E. Johnson, and J. D. Rush, Mössbauer and Electrochemical Studies on Fe3MoS4 and Fe3WS4 Cubane-Like Cluster Dimers, J. Chem. Soc. (Dalton), 2364 (1980).Google Scholar
  39. 38.
    S. R. Acott, C. D. Garner, and C. J. Pickett, unpublished results.Google Scholar
  40. 39.
    M. W. W. Adams, K. K. Rao, D. O. Hall, G. Christou and C. D. Garner, Biological Activity of Synthetic Molybdenum-Iron-Sulfur, Iron-Sulfur and Iron-Selenium Analogues of Ferre-doxin-Type Centers, Biochim. Biophys. Acta 589:1 (1980).PubMedCrossRefGoogle Scholar
  41. 40.
    G. Christou, R. V. Hagenan, and R. H. Holm, Hydrogen Evolution from Homogeneous Reaction Systems Containing Reduced Mo-Fe-S Clusters, J. Am. Chem. Soc. 102:7600 (1980).CrossRefGoogle Scholar
  42. 41.
    G. Christou, D. Collison, C. D. Garner, F. E. Mabbs, and V. Petrouleas, Spin-Exchange Interactions in Cubane-Like Cluster Dimers [NEt4]3[Fe6M2S8(SPh)6(OMe)3] (M = Mo or W), Inorg. Nucl. Chem. Letters 17:137 (1981).CrossRefGoogle Scholar
  43. 42.
    D. Collison, C. D. Garner, F. E. Mabbs and V. Petrouleas, unpublished results.Google Scholar
  44. 43.
    J. Rawlings, V. K. Shah, J. R. Chisnell, W. J. Brill, R. Zimmermann, E. Münck, and W. H. Orme-Johnson, Novel Metal Cluster in the Iron-Molybdenum Cofactor of Nitrogenase; Spectroscopic Evidence, J. Biol. Chem. 253:1001 (1978).PubMedGoogle Scholar
  45. 44.
    R. H. Holm and J. A. Ibers, Synthetic Analogues of the Active Sites of Iron-Sulfur Proteins in: “Iron-Sulfur Proteins,” W. Lovenberg, ed., Academic Press, New York, Vol. III, p. 206 (1977).Google Scholar
  46. 45.
    S. R. Acott, D. Collison, C. D. Garner and F. E. Mabbs, unpublished results.Google Scholar

Copyright information

© Plenum Press, New York 1983

Authors and Affiliations

  • C. David Garner
    • 1
  • Stephen R. Acott
    • 1
  • George Christou
    • 1
  • David Collison
    • 1
  • Frank E. Mabbs
    • 1
  • Vasili Petrouleas
    • 1
    • 2
  • Christopher J. Pickett
    • 1
    • 3
  1. 1.Department of ChemistryManchester UniversityManchesterUK
  2. 2.Physics DivisionNuclear Research Center DemokritosAttikiGreece
  3. 3.A.R.C. Unit of Nitrogen FixationUniversity of SussexBrighton, SussexUK

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