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Advances in Solution Chemistry pp 105–114Cite as

Mechanism of Octahedral Substitutions on Transition Metal Complexes. Attempts to Distinguish Between D and Id Mechanisms

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Abstract

The evidence obtained from studying the induced aquations of Co(NH3)5N3 2+ and of Co(NH3)5(O2CNH2)2+ by nitrous acid, and of Co(NH3)5(halide)2+ by Hg2+, led to the conclusion that a common five-coordinate intermediate, Co(NH3)5 3+, was formed in all these reactions. Recent examinations of different reactions, including KMnO4 induced aquation of Co(NH3)5(DMSO)3+, however, suggest different intermediates in different reactions. The mechanism of several octahedral replacement reactions, studied in our laboratory, is discussed. These reactions are: aquations of trans-chloronitro- and trans-dichlorobisethylene- diaminecobalt(III) ions, and of (dimethyl suphoxide) pentaammi- necobalt(III) ions, in mixed aqueous-organic solvents; base-hydrolysis of Co(NH3)5(DMSO)3+; anations of Fe(CN)5(H2O)3- ion; replacements in FeII(CN)5(ligand)n- ions; replacements in the binuclear dimer of Fe(CN)5(H2O)3-. It was shown that often there is no sharp distinction between D and Id mechanism. The clear-cut D mechanism is much less frequent than it was originally thought to be the case. In the reaction systems mentioned the kinetic results are more consistent with Id than with D mechanism.

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Author information

Authors and Affiliations

  1. Department of Chemistry, Faculty of Pharmacy and Biochemistry, University of Zagreb, Zagreb, Croatia, Yugoslavia

    Smiljko Ašperger

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  1. Smiljko Ašperger
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Editors and Affiliations

  1. University of Florence, Florence, Italy

    I. Bertini  & A. Dei  & 

  2. University of Bologna, Bologna, Italy

    L. Lunazzi

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© 1981 Plenum Press, New York

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Ašperger, S. (1981). Mechanism of Octahedral Substitutions on Transition Metal Complexes. Attempts to Distinguish Between D and Id Mechanisms. In: Bertini, I., Lunazzi, L., Dei, A. (eds) Advances in Solution Chemistry. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-3225-1_7

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  • DOI: https://doi.org/10.1007/978-1-4613-3225-1_7

  • Publisher Name: Springer, Boston, MA

  • Print ISBN: 978-1-4613-3227-5

  • Online ISBN: 978-1-4613-3225-1

  • eBook Packages: Springer Book Archive

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