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Dinitrogen Complexes and Their Reactions

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Nitrogen Fixation

Abstract

Dinitrogen complexes have been investigated, since their initial discovery some 15 years ago,1 in order to gain information on the way in which dinitrogen might bind to and be reduced at a metal site, such as is generally accepted to occur in nitrogenase.

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References

  1. A. D. Allen and C. V. Senoff, Nitro genopentammineruthenium(II) Complexes, Chenu Comm. 621 (1965).

    Google Scholar 

  2. J. Chatt, J. R. Dilworth, and R. L. Richards, Recent Advances in the Chemistry of Nitrogen Fixation, Chem. Rev. 780:509 (1978);

    Google Scholar 

  3. A. J. L. Pombeiro, Preparation, Structure, Bonding and Reactivity of Dinitrogen Complexes, in: “New Trends in the Chemistry of Nitrogen Fixation,” J. Chatt, L. M. da Câmara Pina and R. L. Richards eds., Academic Press, London, p. 153 (1980).

    Google Scholar 

  4. G. N. Schrauzer, Studies of the Mechanism of Biological Nitrogen Fixation with Functional Model Systems, in: “New Trends in the Chemistry of Nitrogen Fixation,” J. Chatt, L. M. da Câmara Pina and R. L. Richards, eds., Academic Press, London, p. 103 (1980).

    Google Scholar 

  5. A. E. Shilov, Comparison of Biological Nitrogen Fixation with its Chemical Analogues, in: “New Trends in the Chemistry of Nitrogen Fixation,” J. Chatt, L. M. da Câmara Pina and R. L. Richards, eds., Academic Press, London, p. 121 (1980).

    Google Scholar 

  6. M. Aresta and A. Sacco, Dinitrogen, Carbonyl and Hydrido-Complexes of Molybdenum, Gazz. Chim. Ital. 102:155 (1972).

    Google Scholar 

  7. J. Chatt, R. H. Crabtree, J. R. Dilworth and R. L. Richards Tris(dimethylphenylphosphine)(dinitrogen)(dithiocarbamato) Rhenium Complexes and their Reactions with Hydrogen Halides, J. C. S. (Dalton) 2358 (1974).

    Google Scholar 

  8. C. A. Ghilardi, S. Midollini, L. Sacconi and P. Stoppioni, Hydrido-dinitrogen and Hydrido-Complexes of Iron(II) with Linear Tetratertiary Phosphine Hexaphenyl-1,4,7,10-tetraphos-phadecane, J. Organometal. Chem. 205:193 (1981).

    Article  CAS  Google Scholar 

  9. V. B. Shur, I. A. Tikhonova, G. G. Aleksandrov, Yu. T. Struchkov, M. E. Vol’pin, E. Schmitz and K. Janisch, The Diazirine complex [(NH3)5Ru(N2C6H10)]2+. Inorg. Chim. Acta 44:L275 (1980).

    Article  Google Scholar 

  10. J. D. Buhr and H. Taube, Oxidation of [Os(NH3)5(CO)]2+ to [{Os(NH3)4(CO)}2N2]4+, Inorg. Chem. 18:2208 (1979);

    Article  CAS  Google Scholar 

  11. J. D. Buhr and H. Taube, Dinitrogen Complexes of Osmium(III) Haloammines, Inorg. Chem. 19: 2425 (1980).

    Article  CAS  Google Scholar 

  12. F. Pettit, C. Arzouyin, G. Peiffer and E. Gaydou, Etude de L’Isomerisation due Methyl-5-Pentene-l par [CoH(N2)(PPh3)3], J. Organometal. Chem. 208:261 (1981).

    Article  Google Scholar 

  13. F. K. Schmidt, L. O. Kindakova, S. M. Krasnopol’skaya, N. G. Devyatko, T. V. Dmitrieva and G. V. Ratovskii, Investigation of Isomerisation of α-Olefins by [Co(N2)(PPh3)3], Kin. i Kat. 19:111 (1978).

    Google Scholar 

  14. Y. Miura and A. Yamamoto, Novel Dinitrogen-Cobalt Complexes [Co(N2)(PR3)3Mg(thf)2] which Liberate Hydrazine on Hydrolysis, Chem. Letters 937 (1981).

    Google Scholar 

  15. G. Le Ny, A. E. Shilov, A. K. Shilova and B. Tchoubar, Etude Cinétique due Mechanism de Reduction de L’Azote Moléculaire dans le Sytème: FeCl3 + LiPh + N2, Nouv. J. Chim. 1:397 (1977).

    Google Scholar 

  16. Y. Yoshida, T. Okama and S. Otsuka, Hydrogenation of Nitriles and Dehydrogenation of Amines with [RhHCPPri 3)3] and [Rh2H2(μ-N2){P(cyclohexyl)3}4], J. C. S. Chem. Comm. 870 (1979).

    Google Scholar 

  17. R. Hammer, H- F. Klein, P. Friederich and G. Huttner, Hexameric KN2Co(PMe3)3 — A Novel Potassium-Dinitrogen Cluster, Angew. Chem. Int. Ed. Eng. 16:485 (1977).

    Article  Google Scholar 

  18. D. L. Thorn, T. H. Tulip and J. A. Ibers, The Structure of trans-chloro(dinitrogen)bis(tri-isopropylphosphine) rhodium(I), J. C. S. (Dalton) 2022 (1979).

    Google Scholar 

  19. M. E. Vol’pin and V. B. Shur, Fixation of Molecular Nitrogen in Aprotic Media, in: “New Trends in the Chemistry of Nitrogen Fixation,” J. Chatt, L. M. da Câmara Pina and R. L. Richards, eds., Academic Press, London, p. 67 (1980).

    Google Scholar 

  20. J. H. Teuben, Reactions of Ligating Dinitrogen in Dinuclear Complexes, ibid., p. 233.

    Google Scholar 

  21. R. D. Sanner, J. M. Manriquez, R. E. Marsh, and J. E. Bercaw, Structure of μ-Dinitrogen-bis(bis(pentamethylcyclopentadienyl dinitrogenzirconium(II)), [(η 5-C5(CH3)5}2ZrN2]2N2, J. Am. Chem. Soc. 98:8351 (1976).

    Article  CAS  Google Scholar 

  22. J. M. Manriquez, D. M. McAllister, E. Rosenberg, A. M. Shiller, K. L. Williamson, S. I. Chan and J. E. Bercaw, Solution Structure and Dynamics of Binuclear Dinitrogen Complexes of Ti(C5Me5)2 and Zr(C5Me5)2 J. Am. Chem. Soc. 100:3078 (1978) and references therein.

    Article  CAS  Google Scholar 

  23. J. Jeffery, M. F. Lappert and P. I. Riley, Organozirconium Dinitrogen Complexes [Zr(η-C5H4R’)22-N2)R] and [{Zr(η-C5H5)2 R}2N2] [R = (Me3Si)2CH, R’ = H or Me] J. Organometal. Chem. 181:25 (1979).

    Article  CAS  Google Scholar 

  24. L. A. Nikonova, S. Runvarel, A. E. Shilov and M. Wahren, Is Diimide an Intermediate in Dinitrogen Reduction by V(II) Complexes in Protic Media?, Nouv. J. Chim. 4:427 (1980).

    CAS  Google Scholar 

  25. D. A. Lemenovskii, T. A. Baukova, E. G. Perevalova and A. N. Nesmeyanov, The Fixation of Molecular Oxygen and Nitrogen by an Organometallic Complex of Nb(IV) Izvest. Akad. Nauk. SSSR. Ser. Chem. 10:2404 (1976).

    Google Scholar 

  26. R. J. Burt, D. L. Hughes and G. J. Leigh, Carbonyl Complexes of Niobium and Tantalum and Evidence of a Niobium Dinitrogen Complex, J. C. S. (Dalton) 793 (1981).

    Google Scholar 

  27. H. W. Turner, J. D. Fellmann, S. M. Rocklage, R. R. Schrock, M. R. Churchill and H. J. Wasserman, Tantalum Complexes Containing Diimido Bridging Dinitrogen Ligands, J. Am. Chem. Soc. 102:7809 (1980).

    Article  CAS  Google Scholar 

  28. H. H. Karsch, cis-Bis(dinitrogen)tetrakis(trimethylphosphine) chromium, Angew. Chem. Int. Ed. Engl. 16:56 (1977).

    Article  Google Scholar 

  29. P. Sobota and B. Jezowska-Trzebiatowska, Fixation of Dinitrogen and Acetylene by the System CrCl2-Mg, J. Organometal. Chem. 131:341 (1977).

    Article  CAS  Google Scholar 

  30. B. J. Weathers, J. H. Grate, N. A. Strampach and G. N. Schrauzer, Chemical Evolution of a Nitrogenase Model.18. Reduction of Molecular Nitrogen with Molybdo-insulin Catalysts, J. Am. Chem. Soc. 101:925 (1979).

    Article  CAS  Google Scholar 

  31. S. N. Anderson, J. Chatt, M. E. Fakley and R. L. Richards, Hydrazido(2-)-complexes as Intermediates in the Conversion of Ligating Dinitrogen into Ammonia and Hydrazine, J. C. S. (Dalton) in the press (1981).

    Google Scholar 

  32. J. Chatt, M. E. Fakley, J. Mason, R. L. Richards and I. A. Stenhouse, 15N NMR Spectroscopic Studies of Dinitrogen Complexes of Molybdenum and Tungsten, J. Chem. Research(M) 0873 (1979); 15 N NMR Spectroscopic Studies on Hydrazido(2-)-Complexes of Molybdenum and Tungsten, J. Chem. Research (M), 3701 (1979).

    Google Scholar 

  33. J. R. Dilworth, S. Donovan-Mtunzi, C. T. Kan, J. Mason and R. L. Richards, 15N NMR Spectra of Metal Complexes Relevant to Nitrogen Fixation, Inorg. Chim. Acta 53:L161 (1981); S. Donovan-Mtunzi, J. Mason, R. L. Richards and I. A. Stenhouse, unpublished results.

    Article  CAS  Google Scholar 

  34. T. Takahashi, Y. Mizobe, M. Sato, Y. Uchida and M. Hidai, Protonation Reactions of Molybdenum and Tungsten Dinitrogen Complexes with Halogen Acids, J. Am. Chem. Soc. 102:7461 (1980).

    Article  CAS  Google Scholar 

  35. J. R. Dilworth, R. A. Henderson, G. J. Leigh, C. J. Pickett and R. L. Richards, How is Dinitrogen Converted to Ammonia on Molybdenum? in: “Current Perspectives in Nitrogen Fixation,” A. H. Gibson and W. E. Newton, eds., Australian Academy of Science, Canberra, Australia, p. 349 (1981).

    Google Scholar 

  36. J. A. Baumann and T. A. George, Formation of Ammonia by Protonation of a Molybdenum-Dinitrogen Complex and Isolation and Characterization of the Molybdenum-Containing Product, J. Am. Chem. Soc. 102:6153 (1980).

    Article  CAS  Google Scholar 

  37. J. Chatt, M. E. Fakley, I. R. Hanson, D. L. Hughes and R. L. Richards, The influence of Ligand Environment on the Protonation Reactions of Hydrazido(2-)-Complexes of Molybdenum and Tungsten: X-Ray Structure of [M(8-quin)(NNH2)(PMe2Ph)3]I M = Mo or W; 8-quin = quinolin-8-olate), J. Organometal. Chem. 170:C6 (1979).

    Article  CAS  Google Scholar 

  38. R. Periantozzi and G. L. Geoffroy, Photoinduced Elimination of H2 from [MoH4(dppe)2] and [MoH4(PPh2Me)4], Inorg. Chem. 19:1821 (1980).

    Article  Google Scholar 

  39. H. Nishikara, T. Mori, T. Saito and Y. Saskai, Reduction of Coordinated Dinitrogen in cis-[W(N2)2(PMe2Ph)4] by Means of Acidic Hydridometal Carbonyls, H2Fe(CO)4 and HFeCo3(CO)12, Chem. Letters 667 (1980).

    Google Scholar 

  40. J. Chatt, M. E. Fakley, P. B. Hitchcock, D. L. Hughes, N. Tuyet Lûong-Thi and R. L. Richards, Hydrazido(2-)-(or Isodiazene)-Complexes of Tungsten, J. Organometal. Chem. 172:C55 (1979).

    Article  CAS  Google Scholar 

  41. J. Chatt, A. J. L. Pombeiro and R. L. Richards, Hydrido-Complexes of Molybdenum and Tungsten with Isonitrile and Carbyne-type Ligands, J. C. S. (Dalton) 1585 (1979).

    Google Scholar 

  42. S. N. Anderson and R. L. Richards, unpublished results.

    Google Scholar 

  43. J. Chatt, W. Hussain, G. J. Leigh, H. Neukomm, C. J. Pickett and D. A. Rankin, The Mechanism of the Secondary Alkylation of Dinitrogen and the Relationship between Structure and Reactivity in the Alkylation of Coordinated Dinitrogen, J. C. S., Chem. Comm. 1024 (1980) and references therein.

    Google Scholar 

  44. R. Ben-Shoshan, J. Chatt, G. J. Leigh and W. Hussain, Diazoalkane Complexes and Related Compounds from Reactions of Dinitrogen Complexes of Tungsten and Molybdenum with gem-Dibromides and from Condensation of Hydrazido(2-)-Complexes with Aldehydes, J. C. S. (Dalton), 771 (1980) and references therein.

    Google Scholar 

  45. P. C. Bevan, J. Chatt, M. Hidai and G. J. Leigh, Diazoalkane Complexes of Tungsten from the Condensation of Hydrazido-Complexes with Ketones, J. Organometal. Chem. 160:165 (1978).

    Article  CAS  Google Scholar 

  46. M. Hidai, Y. Mizobe, T. Takahachi and Y. Uchida, Conversion of Ligating Dinitrogen into Hydrazine, Chem. Letters 1187 (1978).

    Google Scholar 

  47. G. E. Bossard, D. C. Busby, M. Chang, T. A. George, and S. D. A. Iske, Reactions of Bromoalkanes with [Mo(N2)2(dppe)2]. Formation of Ammonia and Amines, J. Am. Chem. Soc. 102:1001 (1980).

    Article  CAS  Google Scholar 

  48. G. J. Leigh and C. J. Pickett, unpublished observations.

    Google Scholar 

  49. J. Chatt, G. J. Leigh, H. Neukomm, C. J. Pickett and D. R. Stanley, Redox Potential-Structure Relationships in Metal Complexes, J. C. S. (Dalton) 121 (1980).

    Google Scholar 

  50. C. J. Pickett, A. J. L. Pombeiro, R. L. Richards and S. A. Sangokoya, Mechanism of Displacement of Dinitrogen from cis-[Mo(N2)2(PMe2Ph)4] and trans-[Mo(N2)2(dppe)2] by Isocyanides, J. Organometal. Chem. 202:C15 (1980) and references therein.

    Google Scholar 

  51. D. Sellman and W. Weiss, Consecutive Nucleophilic and Electrophilic Attack on N2 Ligands, Angew. Chem. Int. Ed. Engl. 17:269 (1978).

    Article  Google Scholar 

  52. J. Chatt, G. J. Leigh, C. J. Pickett and D. R. Stanley, Hydroxycarbene Dinitrogen Complex of Rhenium, J. Organometal. Chem. 184:C64 (1980).

    Article  CAS  Google Scholar 

  53. B. E. Smith, D. J. Lowe, J. R. Postgate, R. L. Richards and R. N. F. Thorneley, Studies on N2 Reduction by Nitrogenase from Klebsiella pneumoniae, in: “Current Perspectives in Nitrogen Fixation,” A. H. Gibson and W. E. Newton, eds., Australian Academy of Science, Canberra, Australia, p. 67 (1981).

    Google Scholar 

  54. J. Chatt, Towards New Catalysts for Nitrogen Fixation, in: “Current Perspectives in Nitrogen Fixation,” A. H. Gibson and W. E. Newton, eds., Australian Academy of Science, Canberra, Australia, p. 15 (1981).

    Google Scholar 

  55. R. A. Henderson, G. Davies, J. R. Dilworth and R. N. F. Thorneley, Mechanism of Ammonia Formation by Reaction of trans-[Mo(NH)X(dppe)2]+ (X = F, C1, Br or I) with Base in Methanol, J. C. S. (Dalton) 40 (1981).

    Google Scholar 

  56. J. R. Dilworth and J. A. Zubieta, Preparation and X-ray crystal structure of [S2MoS2Mo(NNMe2)2(PPh3)] a binuclear hydrazido(2-)-complex Containing Coordinated Tetrathiomolybdate, J. C. S., Chem. Comm. 132 (1981).

    Google Scholar 

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© 1983 Plenum Press, New York

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Richards, R.L. (1983). Dinitrogen Complexes and Their Reactions. In: Müller, A., Newton, W.E. (eds) Nitrogen Fixation. Springer, Boston, MA. https://doi.org/10.1007/978-1-4684-8523-3_11

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  • DOI: https://doi.org/10.1007/978-1-4684-8523-3_11

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