Aquation of α-cis-chloroaquoethylenediamine-N,N'-diacetatocobalt(III) in aqueous and in mixed solvents: A mechanistic study |
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Authors: | Chinmoy Chatterjee Arup K Basak |
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Institution: | (1) Department of Chemistry, Indian Institute of Technology, Powai, 400076 Bombay, India;(2) Inorganic Chemistry Laboratories, University College of Science, 92, Acharya P. C. Road, 700009 Calcutta, India;(3) Present address: Tokyo Institute of Technology, 227 Yokohama, Japan |
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Abstract: | Summary The displacement of chloride ligands from -cis-chloro-aquoethylenediamine-N,N-diacetatocobalt(III) in nonacidic aqueous solutions was followed conductimetrically at 30–45° and the products of aquation were characterised by conductance, spectral and ion-exchange techniques. The rate constants for aquation in aqueous media and in 1 : 4 v : v mixed solvents at 25° are: 4.0 × 10–5 s–1 in H2O, 2.71 × 10–5 s–1 in MeOH : H2O, 2.74 × 10–5 s–1 in EtOH: H2,O and 2.58 × 10–5 s–1 n in Me2CO : H2O. The corresponding H* and S* values have also been evaluated. Solvent polarity has a marked influence on the rate of chloride ion release. The aquation rate constants and the activation parameters have been correlated with solvent parameters,e.g. D, Y-values, Dimroth's ET and Kosower's Z-values and, based on these correlations, a dissociative interchange (Id) mechanism is proposed rather than dissociative as observed for some other cobalt(III) complexes.Senior author. |
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