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首页> 外文期刊>Bulletin of the Chemical Society of Japan >Kinetics and Mechanism of Tris(pyridine-2-carboxylato)manganese(III) Reduction by Azide Ion in Sodium Pyridine-2-carboxylate-Pyridine-2-carboxylate-Pyridine-2-carboxylic Acid Buffer Media
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Kinetics and Mechanism of Tris(pyridine-2-carboxylato)manganese(III) Reduction by Azide Ion in Sodium Pyridine-2-carboxylate-Pyridine-2-carboxylate-Pyridine-2-carboxylic Acid Buffer Media

机译：吡啶-2-羧酸钠-吡啶-2-羧酸钠-吡啶-2-羧酸缓冲液中叠氮化物离子还原三（吡啶-2-羧基）锰（III）的动力学和机理

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摘要

The kinetics and mechanism of the reduction of tris(pyridine-2-carboxylato)manganese(III) by azide ion in Na-(pic)-picH [where Na(pic) = sodium salt of pyridine-2-carboxylic acid and picH = pyridine-2-carboxylic acid] have been studied. The reaction appears to proceed through the intermediate formation of a hepta-coordinated 1 : 1 complex between [Mn~(III)(pic)_3] and N_3~- ion, which then decomposes to give the free radical (N_3) and diaquabis(pyridien-2-carboxylato)-manganese(II). The free radical N_3 further reacts with [Mn~(III)(pic)_3] to give nitrogen as the product of oxidation. During the reduction, pyridine-2-carboxylate ion is generated and the coordination sphere of the parent complex is altered, thereby indicating that the reaction takes place by an inner-sphere mechanism. The enthalpy change ((#DELTA#)H deg) and change in entropy ((#DELTA#)S deg) associated with the equilibrium step are -61+-4 kJ mol~(-1) and -169+-14 JK~(-1) mol~(-1), whereas the enthalpy of activation ((#DELTA#)H~(not=)) and the entropy of activation ((#DELTA#)S~(not=)) associated with the slowest step are found to be 91+-4 kJ mol~(-1) and 11+-14 JK~(-1) mol~(-1), respectively.
机译：Na-（pic）-picH [其中Na（pic）=吡啶-2-羧酸的钠盐，picH =的叠氮化物离子）还原三（吡啶-2-羧甲基）锰（III）的动力学和机理。吡啶-2-羧酸]已被研究。该反应似乎是通过在[Mn〜（III）（pic）_3]与N_3〜-离子之间形成七配位的1：1络合物的中间体而进行的，然后分解生成自由基（N_3）和diaquabis（吡啶-2-羧基）-锰（II）。自由基N_3进一步与[Mn〜（III）（pic）_3]反应，得到氮作为氧化产物。在还原过程中，生成吡啶-2-羧酸根离子，并且改变了母体配合物的配位球，从而表明该反应是通过内球机理进行的。与平衡步骤相关的焓变（（＃DELTA＃）H deg）和熵变（（＃DELTA＃）S deg）为-61 + -4 kJ mol〜（-1）和-169 + -14 JK 〜（-1）mol〜（-1），而活化的焓（（＃DELTA＃）H〜（not =））和活化的熵（（＃DELTA＃）S〜（not =））与最慢的步长分别为91 + -4 kJ mol〜（-1）和11 + -14 JK〜（-1）mol〜（-1）。

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