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Kinetics and mechanism of acid-catalyzed aquation of carbonato-(1,4,8,5,11-tetra-azacyclotetradecane)cobalt(II) ion

✍ Scribed by T.P. Dasgupta

Publisher: Elsevier Science
Year: 1976
Tongue: English
Weight: 321 KB
Volume: 20
Category: Article
ISSN: 0020-1693
DOI: 10.1016/s0020-1693(00)94086-6

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✦ Synopsis

The acid-catalyzed aquation of the title compound has been studied over the range of O.O5<[H+]<OSM and 40" <T<50" C at I=O.5 M. The pseudo-first-order rate constants are directly proportional to [H+] for the range of acidity studied. The results have been interpreted in terms of mechanism involving acidcatalyzed dechelation followed by a rapid decarboxylation of the monodentate intermediate. At 25" C, the acid-catalyzed ring-opening rate constant, k,, is 1.3 x 1 o-3 M-' set-' and the temperature variations describing this constant are AHY, 20.6 f 0.4 kcallmol and AS' = -2.6 + I.3 calldeg mol. The results are compared with those obtained for similar carbonato (tetramine)cobalt(IlI) complexes.

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