Kinetics and mechanism for the aquation of bismalonatoethylenediaminecobaltate(III) ion in acid perchlorate media |
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Authors: | Sarmistha Das Samirgopal Bhattacharya Rupendra Nath Banerjee Debabrata Banerjea |
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Affiliation: | (1) Department of Chemistry, Inorganic Chemistry Division, University College of Science, 92, Acharya Prafulla Chandra Road, 700009 Calcutta, India |
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Abstract: | Summary The title complex aquates in acid media, first to [Co(mal)-(H2O)2(en)]+ (1) (Step 1) and subsequently to [Co(H2O)4(en)]3+(2) (Step 2). Complex species (1) has been separated and characterised in solution. While Step 1 involves only a second-order acid catalysed path, Step 2 involves both a first-order acid independent path and a second-order acid catalysed path. The rate constants and activation parameters evaluated for these reaction paths have been compared with those for similar carboxylato-cobalt(III) complexes. This, together with an observed isokinetic relation, indicates that the rate-determining step involves opening of the unprotonated (in the spontaneous acid independent path) or the protonated (for the acid catalysed path) chelate ring of the malonate ligand and insignificant solvation of the central metal ion. |
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