Issue 2, 1987

Solvent-exchange reactions of metal ions. Diagnosis of mechanisms in terms of the bond order of the activated complexes

Abstract

An intersecting-state model has been applied to calculate activated complex bond orders, n, in water-exchange reactions of metal ions. Under the assumption that metal–water bond-breaking–bond-forming processes have a concerted nature and the bonds have a harmonic behaviour, n is found to vary continuously from 0.5 to 1.0. Reaction mechanisms, assessed in terms of n and ΔV, reveal that solvent-exchange mechanisms present a continuum between n= 0.5 and 1.0 and dissociative and associative extremes. The extreme cases are an outer-shell association process, A(n= 0.5, ΔV≪ 0), an inner-shell association Ai(n≈ 1.0, ΔV+≪ 0) and an inner-shell dissociation, Di(n= 1.0, ΔV≫ 0). For the normal dissociation of a water–metal bond, D, 0 [graphic omitted] n < 0.5. However, nonharmonic behaviour has to be employed to estimate n. Correlations between different types of mechanism and electronic structure are established. Data in some non-aqueous solvents are briefly discussed.

Article information

Article type
Paper

J. Chem. Soc., Faraday Trans. 1, 1987,83, 431-438

Solvent-exchange reactions of metal ions. Diagnosis of mechanisms in terms of the bond order of the activated complexes

S. J. Formosinho, J. Chem. Soc., Faraday Trans. 1, 1987, 83, 431 DOI: 10.1039/F19878300431

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