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The limiting dissociative mechanism for substitution at thed 6 centres molybdenum(O), iron(II), and cobalt(III): Kinetics of substitution at the pentacyano-4-Cyanopyridineferrate(II) anion and at 4-cyanopyridinemolybdenum(I) pentacarbonyl

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Summary

Rate constants are reported for reaction of the 4-cyanopyridine complexes [Fe(CN)5(4CNpy)]3− and [Mo(CO)5(4CNpy)] with a variety of incoming ligands, in aqueous methanol (40 vol % MeOH) and in toluene respectively, at 298.2 K (ambient pressure). The dependence of rate constants on the nature and concentration of the incoming ligand is discussed in terms of the operation of the limiting dissociative,D, mechanism for substitution; the operation of this mechanism here, and in analogous pentacyanoferrate(II), pentacarbonylmolybdenum(I), and penta- and tetra-cyanocobaltate(III) complexes is reviewed. The effect of pressure on rate constants for replacement of 4-cyanopyridine in [Mo(CO)5(4CNpy)], in toluene solution at 298.2 K, indicates an activation volume of +3 cm3 mol−1.

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Author notes

  1. Ezz-Eldin A. Abu-Gharib

    Present address: Faculty of Science, Sohag, Egypt

  2. Razak bin Ali

    Present address: Chemistry Department, University of Technology, Gurney Road, Kuala Lumpur, Malaysia

Authors and Affiliations

  1. Chemistry Department, University of Leicester, LEI 7RH, Leicester, UK

    Ezz-Eldin A. Abu-Gharib, Razak bin Ali, Michael J. Blandamer & John Burgess

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  1. Ezz-Eldin A. Abu-Gharib
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  2. Razak bin Ali
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  3. Michael J. Blandamer
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  4. John Burgess
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Abu-Gharib, EE.A., Ali, R.b., Blandamer, M.J. et al. The limiting dissociative mechanism for substitution at thed 6 centres molybdenum(O), iron(II), and cobalt(III): Kinetics of substitution at the pentacyano-4-Cyanopyridineferrate(II) anion and at 4-cyanopyridinemolybdenum(I) pentacarbonyl. Transition Met Chem 12, 371–378 (1987). https://doi.org/10.1007/BF01024038

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