Kinetics and mechanism of the anation of cis (aquo)(ammine) bis(ethylenediamine) Co(III) by oxalate |
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| Affiliation: | 1. Department of Chemistry, Faculty of Sciences, Sakarya University, 54187 Sakarya, Turkey;2. Department of Chemistry, Faculty of Arts and Sciences, Hitit University, Çorum, Turkey;1. Key Laboratory of Chemical Biology and Molecular Engineering of Education Ministry and Key Laboratory of Energy Conversion and Storage Materials of Shanxi Provence, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China;2. Institute of Coal Chemistry, Chinese Academy of Sciences,Taiyuan 030001, China;3. Techinical Institute of Physics & Chemistry, CAS, Beijing 100190, China;4. Department of Engineering Science, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu-shi, Tokyo 182-8585, Japan |
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| Abstract: | The kinetics of the anation of cis (aquo)(ammine)bis(ethylenediamine)Co(III) by H2C2O4, HC2O4− and C2O42− have been investigated at 50–60°C and I = 1.0 mol dm−3 (ClO4−). Association of the aquo cation with oxalic acid could not be identified. The association constants of the aquo-HC2O4− and aquo-C2O42− ion-pairs are essentially temperature independent and have values 1.5 and 5.8 dm3 mol−1 (50–60°C) respectively. The interchange reactions of the ion-pairs to yield the innersphere complexes, cis[(en)2(NH3)CoC2O4]+ or its acid form, are assigned a dissociative mechanism, Id, involving CoO bond breaking. The mechanism of the anation of the aquo cation by H2C2O4 may be Id but the possibility of rate limiting addition of oxalic acid to the CoO bond can not be completely ruled out. |
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