Abstract
Abstract The proton-transfer reactions of bis(dimethylglyoximato)cobalt(III) complex ions, [CoIII(dmgH)2X2]n, with hydroxide ion, OH−, were studied in dioxane–water media by means of a temperature-jump method. The rate constant, kf, for the direct proton-transfer from [CoIII(dmgH)2X2]n to OH− was found to be 1.6×105–2.9×106 mol−1 dm3 s−1 in aqueous solution. The value of kf for [CoIII(dmgH)2(CN)2]− anion decreased gradually from 1.6×105 to 4.0×104 mol−1 dm3 s−1 for the change in the mole fraction of dioxane, xdiox, from 0 to 0.174. On the other hand, with increase in xdiox, the value of kf for [CoIII(dmgH)2(NH3)2]+ cation gradually decreased from 2.9×106 to 1.1×107 mol−1 dm3 s−1 in a region of lower xdiox, and then increased from 1.1×106 to 1.6×106 mol−1 dm3 s−1 in a region of higher xdiox. The dependence of kf on xdiox is interpreted in connection with reaction mechanism.
Published Version
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