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Mechanism of Metal Ion Catalysis in the dissociation of cis‐diaquobisoxalatochromate(III) ion
L GOSWAMI, S SARKAR, D BANERJEA
Published in -
1977
Volume: 435
   
Issue: 1
Pages: 301 - 304
Abstract
The metal ion (M2+) catalysed dissociation of cis‐diaquobisoxalatochromate into the tetraaquomonooxalato complex in aqueous perchloric acid medium which follows the rate law — d(complex)/dt = {kH[H+] + kM[M2+]}[complex] has been studied. Based on kM values the order of catalysing effect of the different metal ions studied is Cu2+ > Ni2+ > Co2+ > Mn2+, which is also the order of stabilities (KMOx) of the monooxalato complexes of these metal ions; in fact the plot of log kM vs. log KMOx is linear. This together with the relative values of ΔH≠ and ΔS≠ for the H+ catalysed and M2+ catalysed paths is in agreement with a mechanism involving chelation of the catalysing cation through the free carbonyl oxygens of the oxalate ligand bound to Cr(III), followed by the dissociation of the Cr(III)O bonds with simultaneous entry of two water molecules into the coordination sphere of Cr(III). Copyright © 1977 Verlag GmbH & Co. KGaA, Weinheim
About the journal
JournalZAAC ‐ Journal of Inorganic and General Chemistry
Publisher-
ISSN0044-2313