Kinetics and mechanism of acid and base hydrolysis ofcis-chloro-(benzotriazole)bis(ethylenediamine)cobalt(III) andcis-chloro-(N-methylbenzotriazole)bis(ethylenediamine)cobalt(III) cations |
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Authors: | B. Seshagiri Rao Rabindranath Nanda Kumuda Kanta Tripathy |
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Affiliation: | (1) Department of Chemistry, Ravenshaw College, 753003 Cuttack, India;(2) Christ College, Cuttack, India |
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Abstract: | Summary The kinetics of acid hydrolysis ofcis-[CoCl(btzH)(en)2]2+ andcis-[CoCl(btzMe)(en)2]2+ complexes (where btzH = benzotriazole, btzMe =N-methylbenzotriazole and en = ethylenediamine) have been investigated in HClO4 at ionic strength 1 = 0.25 mol dm–3 in the 30–40° range. In the 1.0 x 10–1 to 1.0 X 10–3 mol dm–3 acid strength range, the rate of aquation of the [CoCl(btzH)(en)2]2+ cation follows the relationship:-d ln[complex]/dt = k1 + k2KNH[H+]–1, where k1 and k2 are aquation rate constants of the acid independent and acid dependent steps respectively, and KNH is the acid dissociation constant of the coordinated benzotriazole.cis-[CoCl(btzMe)-(en)2]2+ undergoes acid independent hydrolysis presumably due to the absence of a labile N-H proton. The base hydrolysis could be followed for thecis-[CoCl(btzMe)(en)2]2+ complex only by measuring hydrolysis rates at 0°. |
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