μ-过氧桥接双核琥珀酰亚胺钴(III)配合物在盐酸水溶液中氧化赖氨酸的动力学研究

A. Adetoro, S. Idris, A. D. Onu, F. Okibe
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引用次数: 1

摘要

μ-过氧双[双(乙二胺)琥珀酰咪唑二钴(III)]二水合二硝酸钠氧化赖氨酸的动力学及机理在氢离子浓度为1.8 × 10−2 mol dm−3,温度为24±1℃,[LCo(μ-O2)CoL2+] = 1.4 × 10−4 mol dm−3,离子强度为0.5 mol dm−3的条件下,在420 nm波长处研究了配合物[LCo(μ-O2)CoL](NO3)2.2H2O (L = suc(en)2))的最大吸收。[LCo(μ-O2)CoL2+]和[Lys]为一阶,[H+]为反一阶。总速率方程为:rate =(k1k2+K1k3k41[H+])[LCo(μO2)CoL2+][Lys] $$Rate = ({{k_1 } \over {k_2 }} + {{K_1 k_3 } \over {k_4 }}{1 \over {[H^ + ]}})[LCo(\mu O_2 )CoL^{2 + } ][Lys]$$在0.1 ~ 1.3 mol dm−3范围内,反应速率随氢离子浓度的增加而降低,随离子强度浓度的增加而相反。添加的阳离子和阴离子影响反应速率,Michaelis-Menten图穿过原点,表明在电子转移过程中不存在中间络合物。综合所得到的结果,最可能的反应机理是外球反应,并利用稳态近似建立了合适的速率定律。
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The Kinetics of the Oxidation of Lysine by μ-Peroxo-Bridged Binuclear Cobalt (III) Complex of Succinimide in Aqueous Hydrochloric Acid Medium
Abstract Kinetics of oxidation of Lysine (Lys) and mechanisms by μ-peroxo bis[bis(ethylenediamine)succinimidato-dicobalt(III)]dinitratedihydrate; [LCo(μ-O2)CoL](NO3)2.2H2O (L = suc(en)2), hereafter the complex, was investigated at 420 nm wavelength of maximum absorption of the complex under the conditions hydrogen ions concentration = 1.8 × 10−2 mol dm−3, temperature = 24 ± 1 °C, [LCo(μ-O2)CoL2+] = 1.4 × 10−4 mol dm−3 and ionic strength = 0.5 mol dm−3. First order in [LCo(μ-O2)CoL2+] and [Lys] were obtained but inverse first order in [H+]. The proposed overall rate equation is as shown: Rate=(k1k2+K1k3k41[H+])[LCo(μO2)CoL2+][Lys] $$Rate = ({{k_1 } \over {k_2 }} + {{K_1 k_3 } \over {k_4 }}{1 \over {[H^ + ]}})[LCo(\mu O_2 )CoL^{2 + } ][Lys]$$ Rate of the reaction decreases when hydrogen ions concentration increase and exhibited converse effect with increase in concentration of ionic strength from 0.1 – 1.3 mol dm−3. Added cations and anions affected the reaction rate and the Michaelis-Menten plot passed through the origin indicating no absence of intermediate complex in the electron transfer processes. Putting all the results obtained together, the most probable reaction mechanism is in favour of outer-sphere and an appropriate rate law is established using steady state approximation.
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