Equilibria in complexes ofN-heterocyclic molecules,part XXXI. an explanation for rates of dissociation of iron(II) complexes of diimine ligands |
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Authors: | Robert D. Gillard David W. Knight Peter A. Williams |
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Affiliation: | (1) Department of Chemistry, University College, Cardiff CFI IXL, P.O. Box 78, Wales, UK |
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Abstract: | Summary [Fe(3,3'-bipyridazine)3]2+ has a negligible rate of dissociation in water at pH 7, and in 0.05 mol dm–3 HO– at ionic strength 1.00 mol dm–3 (NaNO3) at 298.2 K, the second-order rate constant involving HO– is only 3.3 x 10–5 dm3 mol–1 s–1. Examination of kinetic and other data and results for it wide variety oftris-diimine complexes of FeII related compounds, indicates that dissociation takes placevia attack at the ligand. The significance of the various possible intermediates is assessed and it is evident that a previously postulated intramolecular transfer of HO– from the ligand to the metal atom, with associated metal-nitrogen bond fission, is important in the reaction. A general scheme for dissociation of these kinds of compounds is set out.Part XXX: R. D. Gillard, R. P. Houghton and J. N. Tucker,J. Chem. Soc., Dalton Trans., submitted for publication.Present address: Department of Chemistry. University of Nottingham, University Park, Nottingham NG7 2RD U.K. |
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