Summary
The pressure dependencies of spontaneous and acid-catalyzed ring-opening, and subsequent decarboxylation reactions were studied for the complexes Co(en)2CO +3 , α- and β-Co-(edda)CO −3 and Co(nta)CO 2−3 . The volumes of activation for the spontaneous ring-opening process of the anionic carbonato complexes areca. 10 cm3 mol−1 more negative than those for the corresponding acid-catalyzed process, and are ascribed to the increase in electrostriction around the free end of the carbonate ligand produced during the dissociative ring-opening step. The absence of such a difference for the Co(en)2CO +3 species and the magnitude of the volumes of activation suggest a ring-opening mechanism of the Ia type. No significant pressure effects were observed for the decarboxylation reactions. A plausible explanation is offered.
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15.7.1955–4.8.1982.
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van Eldik, R., Spitzer, U. Effect of pressure on the aquation reactions of a series of bidentate carbonato-complexes of CoIII in aqueous solution. Transition Met Chem 8, 351–354 (1983). https://doi.org/10.1007/BF00618571
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DOI: https://doi.org/10.1007/BF00618571