Monatshefte für Chemie / Chemical Monthly

, Volume 117, Issue 4, pp 429–435 | Cite as

Study on the reactions of the dinitrogen complexestrans-[M(N2)2(Ph2PCH2CH2PPh2)2] (M=Mo or W) with ethyldiazoacetate: Formation of an Azo compound and of a phosphazene species

  • Rudolf Herrmann
  • Armando J. L. Pombeiro
Anorganische Und Physikalische Chemie


Complextrans-[Mo(N2)2(dppe)2] (dppe=Ph2PCH2CH2PPh2) reacts with NN=CHCOOEt in benzene solution to afford benzene-azomethane,Ph-N=N-CH3, as the main organic product. However, the phosphazene speciesPh2P(N2CHCOOEt)(CH2CH2)P(N2CHCOOEt)Ph2 is formed by irradiating aTHF solution oftrans-[W(N2)2(dppe)2] in the presence of ethyldiazoacetate; in moist solution, the phosphazene bonds undergo a partial hydrolysis, and the phosphonium species [Ph2P(NHNCHCOOEt)(CH2CH2)P(NHNCHCOOEt)Ph2]2+ appears to be formed.


Catalysis Dinitrogen complexes Ethyldiazoacetate 

Untersuchungen zu den Reaktionen der Distickstoff-Komplexetrans-[M(N2)2(Ph2PCH2CH2PPh2)2] (M=Mo oder W) mit Ethyldiazoacetat: Die Bildung einer Azoverbindung und eines Phosphazens


Die Komplexetrans-[Mo(N2)2(dppe)2] (dppe=Ph2PCH2CH2PPh2) reagieren mit NN=CHCOOEt in benzolischer Lösung zuPh-N=N-CH3 als organischem Hauptprodukt. Andererseits wird bei der Bestrahlung vontrans-[W(N2)2(dppe)2] inTHF-Lösung in der Gegenwart von Ethyldiazoacetat das PhosphazenPh2P(N2CHCOOEt)(CH2CH2)P(N2CHCOOEt)Ph2 gebildet; in feuchter Lösung erleidet die Phosphazen-Bindung eine teilweise Hydrolyse und die Phosphonium-Spezies [Ph2P(NHNCHCOOEt)(CH2CH2)P(NHNCHCOOEt)Ph2]2+ scheint gebildet zu werden.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Pombeiro A. J. L., Richards R. L., Trans. Metal Chem.5, 55 (1980);Chatt J., Pombeiro A. J. L., Richards R. L., J. C. S. Dalton1980, 492;Chatt J., Pombeiro A. J. L., Richards R. L., J. C. S. Dalton1979, 1585.Google Scholar
  2. 2.
    Pombeiro A. J. L.,Carvalho M. F. N. N.,Hitchcock P. B.,Richards R. L., J. C. S. Dalton1981, 1629;Pombeiro A. J. L.,Richards R. L.,Dilworth J. R., J. Organometal. Chem.175, C 17 (1979).Google Scholar
  3. 3.
    Pombeiro A. J. L.,Jeffery J. C.,Pickett C. J.,Richards R. L., J. Organometal. Chem.277, C 7 (1984).Google Scholar
  4. 4.
    Hughes D. L.,Pombeiro A. J. L.,Pickett C. J.,Richards R. L., J. C. S. Chem. Comm.1984, 992.Google Scholar
  5. 5.
    See e.g.,Dilworth J. R.,Richards R. L., in: Comprehensive Organometallic Chemistry (Wilkinson G., ed.), Ch. 60. Pergamon Press. 1982.Google Scholar
  6. 6.
    Bevan P. C., Chatt J., Hidai M., Leigh G. J., J. Organometal. Chem.160, 165 (1978).Google Scholar
  7. 7.
    Ben-Shoshan R.,Chatt J.,Leigh G. J.,Hussain W., J. C. S. Dalton1980, 771.Google Scholar
  8. 8a).
    Emsley J.,Hall D., The Chemistry of Phosphorus, Ch. 10. Harper and Row. 1976.Google Scholar
  9. 8b).
    Ibid., Ch. 7.Google Scholar
  10. 9.
    See. e.g.,Pombeiro A. J. L., Preparation, Structure, Bonding and Reactivity of Dinitrogen Complexes, Ch. 6, in: New Trends in the Chemistry of Nitrogen Fixation (Chatt J.,Pina L. M. C.,Richards R. L., eds.). Academic Press. 1980.Google Scholar
  11. 10.
    Archer L. J.,George T. A.,Noble M. E., J. Chem. Ed.1981, 727.Google Scholar
  12. 11.
    Chatt J.,Wedd A. G., J. Organometal. Chem.27, C15 (1971).Google Scholar

Copyright information

© Springer-Verlag 1986

Authors and Affiliations

  • Rudolf Herrmann
    • 1
  • Armando J. L. Pombeiro
    • 1
  1. 1.Centro de Química Estrutural, Complexo IInstituto Superior TécnicoLisboa CodexPortugal

Personalised recommendations