Kinetics of azide attack on organonitriles coordinated to pentaamminecobalt(III)

J. H. Hall, R. Lopez de la Vega, W. L. Purcell

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Abstract

Four new 5-substituted tetrazole complexes of pentaamminecobalt(III) have been synthesized. The N-1 bonded complexes of 5-(p-methylphenyl)tetrazole, 5-(p-chlorophenyl)tetrazole, 5-(p-nitrophenyl)tetrazole and the N-2 bonded complex of 5-(m-formylphenyl)tetrazole. Kinetic studies of the complex formation reaction, wherein azide ion attacks coordinated organonitrile ligands, have been shown to follow a second order rate law, first order in nitrile complex and azide. Rate constants and activation parameters have been determined for five organonitrile complexes and a Hammett type correlation has been established for the formation reaction described by the equation log k = 2.42σ - 2.44 at 25 °C and ionic strength 1.0 M. Two mechanisms are proposed for complex formation which are consistent with our observations.

Original languageEnglish
Pages (from-to)157-162
Number of pages6
JournalInorganica Chimica Acta
Volume102
Issue number2
DOIs
StatePublished - Aug 15 1985

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ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

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