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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >Estimate of the electron exchange rate constant for the 6-molybdocobaltate(III)/(II) couple from studies on the oxidation with iodide using Marcus theory
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Estimate of the electron exchange rate constant for the 6-molybdocobaltate(III)/(II) couple from studies on the oxidation with iodide using Marcus theory

机译：使用马库斯理论从碘化物的氧化研究中估算6-钼二硼酸盐（III）/（II）对的电子交换速率常数

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摘要

The oxidation of the iodide ion by the hexahydrogenhexamolybdocobaltate(III) ion, [(H6CoMo6O24)-Mo-III](3-), having six non-ionisable hydrogen atoms, in perchloric acid at 1 mol dm(-3) ionic strength is first-order with respect to both oxidant and reductant. The rate increases with [H+] and the order with respect to H+ is one in the investigated range of 0.002-0.06 mol dm(-3) The rate of the oxidation is catalysed by H+ and is thus different from the oxidation by the 12-tungstocobaltate(III) ion, [(CoW12O40)-W-III](5-), which is independent of the H+ ion.The reactive species of [(H6COMo6O24)-Mo-III](3-) in acidic solution is considered to be [(HH6CoMo6O24)-Mo-III](2-);the formation of which is supported by repetitive scans of [(H6COMo6O24)-Mo-III](3-) in the presence of perchloric acid.An iodide radical and 6-molybdocobaltate(II) ion are formed.In rapid steps the iodide radical reacts with an iodide ion forming an iodine radical anion which then reacts with another molecule of the heteropoly ion to give iodine, which is immediately converted to the tri-iodide ion in the presence of excess iodide ions.The application of the modified Marcus theory to the present oxidation and by Ni(III)-complexes indicates that the oxidation of the iodide ion is outer-sphere.The estimated value of the self-exchange rate constant for the 6-molybdocobaltate(III)/(II) couple, from the application of the Marcus theory, is 3.5 dm(3) mol(-1) s(-1) and the standard reduction potential (E-0) of the (HCoMo62-)-Mo-III/(HCoMo63-)-Mo-II couple is 1.05 V, determined from measured potentials of cells having different[(HCoMo62-)-Mo-III]/[(HCoMo63-)-Mo-III] ratios with Varying [H+] (0.01-0.05 mol dm(-3)). (c) 2005 Elsevier Ltd. All rights reserved.
机译：在1 mol dm（-3）离子强度下的高氯酸中的六氢六钼六硼酸盐（III）离子[（H6CoMo6O24）-Mo-III]（3-）氧化碘离子的过程是关于氧化剂和还原剂都是一阶的。速率随[H +]的增加而增加，相对于H +的阶数为0.002-0.06 mol dm（-3）的研究范围。氧化速率由H +催化，因此不同于12-钨钴酸根（III）离子[（CoW12O40）-W-III]（5-），它与H +离子无关。考虑了[（H6COMo6O24）-Mo-III]（3-）在酸性溶液中的反应性成为[（HH6CoMo6O24）-Mo-III]（2-）;在高氯酸存在下，通过[[H6COMo6O24）-Mo-III]（3-）的重复扫描来支持其形成。生成6-钼二硼酸盐（II）离子。碘化物自由基与碘离子快速反应，形成碘自由基阴离子，然后与另一个杂多离子分子反应生成碘，碘立即转化为三碘离子。改进的Marcus理论在目前的氧化反应中以及通过Ni（III）络合物的应用表明，碘化物io的氧化n是外球体。根据马库斯理论的应用，6-钼二钴（III）/（II）对的自交换速率常数的估计值为3.5 dm（3）mol（-1）s （-1）和（HCoMo62-）-Mo-III /（HCoMo63-）-Mo-II对的标准还原电势（E-0）为1.05 V，这是由具有不同[[HCoMo62- ）-Mo-III] / [（HCoMo63-）-Mo-III]比与[H +]互不相同（0.01-0.05 mol dm（-3））。 （c）2005 Elsevier Ltd.保留所有权利。

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