Complexation of transition metals by 3-azidopropionitrile. An electrospray ionization mass spectrometry study

  • Narciso Couto
  • M. Filomena Duarte
  • M. Tereza Fernandez
  • Paula Rodrigues
  • M. Teresa Barros
  • M. Lourdes Costa
  • Benedito J. Costa Cabral
Articles

DOI: 10.1016/j.jasms.2006.10.018

Cite this article as:
Couto, N., Duarte, M.F., Fernandez, M.T. et al. J Am Soc Mass Spectrom (2007) 18: 453. doi:10.1016/j.jasms.2006.10.018

Abstract

Most complexes of azides and transition metals involve the N3 azide anion as a ligand other than an organic azide. Complexes of organic azides with metals are involved in biological applications and in the deposition of nitrenes on metal surfaces, producing nitride layers for semi-conductors preparation; this makes the study of these interactions an important issue. This work describes a study of the complexation of nickel and cobalt by 3-azidopropionitrile by means of electrospray ionization mass spectrometry (ESI-MS). Complexes were obtained from solutions of NiCl2 and CoCl2 in methanol/water. In the case of nickel, other NiX2 salts were investigated (where X=Br or NO3) and other solvents were also studied (notably ethanol/water). All complexes detected were single positively charged, with various stoichiometries, some resulted from the fragmentation of the ligand, the loss of N2, and HCN being quite common. The most abundant cations observed were [Ni(II)AzAzX]+, where X=Cl, Br, NO3. Some of the complexes showed solvation with methanol/ethanol/water. Metal reduction was observed in complexes where a radical was lost, resulting from the homolytic cleavage of a metal—nitrogen bond. Collision induced dissociation (CID) experiments followed by tandem mass spectrometry (MS-MS) analysis were not absolutely conclusive about the coordination site. However, terminal ions observed from the fragmentation routes were explained by a proposed gas-phase mechanism. Density functional theory calculations were carried out and provided structures for some complexes, pointing to the possibility of 3-azidopropionitrile acting as a mono- or a bidentate ligand.

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Copyright information

© American Society for Mass Spectrometry 2007

Authors and Affiliations

  • Narciso Couto
    • 1
  • M. Filomena Duarte
    • 1
  • M. Tereza Fernandez
    • 1
  • Paula Rodrigues
    • 3
  • M. Teresa Barros
    • 3
  • M. Lourdes Costa
    • 4
  • Benedito J. Costa Cabral
    • 5
    • 6
  1. 1.CQB, Centro de Química e Bioquímica, Departamento de Química e BioquímicaFaculdade de Ciências da Universidade de LisboaLisboaPortugal
  2. 2.Departamento de Química Bioquímica da Faculdade de Ciências da Universidade de Lisboa and CQBLisboaPortugal
  3. 3.CQFB, Centro de Química Fina e Biotecnologia, Departamento de QuímicaFaculdade de Ciências e Tecnologia da Universidade Nova de LisboaMonte da CaparicaPortugal
  4. 4.CEFITEC, Centro de Física e Investigação Tecnológica, Departamento de FísicaFaculdade de Ciências e Tecnologia da Universidade Nova de LisboaMonte da CaparicaPortugal
  5. 5.Departamento de Química e BioquímicaFaculdade de Ciências da Universidade de LisboaLisboaPortugal
  6. 6.Grupo de Fisica Matemática da Universidade de LisboaLisboaPortugal

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