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Reaction of N N1-phenylenebis(salicyalideneiminato)cobalt(III) and l-cysteine in mixed aqueous medium: kinetics and mechanism

机译:NN1-亚苯基双(水杨酰亚胺基氨基)钴(III)与L-半胱氨酸在混合水性介质中的反应:动力学和机理

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摘要

The redox kinetics involving the reaction of -phenylene (salicyalideneiminato)cobalt(III) ([CoSalophen] ) and l-cysteine (LSH) was studied using pseudo-first order approach under the following conditions, [H ] = 1.0 × 10 mol/dm , μ = 0.1 C mol/dm (NaCl), λ = 470 nm and T = 27 ± 1 °C in DMSO: H O; 1:4 v: v medium. The redox reaction was 1 order in both [CoSalophen ] and [LSH], with the overall 2 order. Hydrogen ion concentration effect revealed the activeness of both the protonated and deprotonated form of the reductant, positive Brønsted-Debye salt effect and was also ion catalyzed. There was no evidence suggesting an intermediate complex of significant stability in the reaction. Free radical was detected to take part and as such the reasonable mechanistic pathway for the reaction is suggested to be outer-sphere, hence proposed.
机译:在以下条件下,使用拟一阶方法研究了涉及-亚苯基(水杨酸亚胺基)钴(III)([CoSalophen])和L-半胱氨酸(LSH)反应的氧化还原动力学。[H] = 1.0×10 mol / dm,在DMSO中,μ= 0.1 C mol / dm(NaCl),λ= 470 nm,T = 27±1°C; 1:4 v:v中。氧化还原反应在[CoSalophen]和[LSH]中均为1级,整体为2级。氢离子浓度效应揭示了质子化形式和去质子化形式的还原剂均具有活性,正布朗斯台德比盐效应也是如此,并且也被离子催化。没有证据表明该反应的中间体复合物具有明显的稳定性。检测到自由基参与其中,因此建议该反应的合理机理是外球。

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