Electron transfer between nickel(IV) oxime-imine complexes and nitrite: kinetics and mechanism

Dutta A.; Banerjee P.; Bhattacharya S.

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Electron transfer between nickel(IV) oxime-imine complexes and nitrite: kinetics and mechanism

机译：肟肟亚胺镍与亚硝酸盐之间的电子转移：动力学和机理

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The oxidation of nitrite ion by two nickel(IV) oxime-imine complexes, [Ni-IV(L-1)](2+) and [Ni-IV(L-2)(2)](2+) (where H2L1 = 3,14-dimethyl-4,7,10,13-tetraazahexadeca dioxime and HL2 = 6-amino-3-methyl-4-azahex-3-en-2-one oxime) has been investigated in aqueous perchlorate medium in the range pH 4.50-7.00 by UV-vis spectrophotometry. The reduction of [Ni-IV(L-2)(2)](2+) involves 2 e(-) transfer (one-step) path at pH less than or equal to 6.0 and above this, it shows biphasic steps involving Ni-III as intermediate. The reduction of [Ni-IV(L-1)](2+) is, however, biphasic in nature throughout the.whole range of pH studied. The reaction rate exhibits a notable dependence on the product Ni-II complex added externally. The experimental findings and the low value of the calculated ion-pair constant suggest that the mode of electron transfer is likely to be of outer-sphere type. (C) 1998 Elsevier Science Ltd. All rights reserved. [References: 22]

机译：两个镍（IV）肟-亚胺络合物[Ni-IV（L-1）]（2+）和[Ni-IV（L-2）（2）]（2+）氧化亚硝酸根离子（其中在高氯酸盐水溶液中研究了H2L1 = 3,14-二甲基-4,7,10,13-四氮杂十六酸二肟和HL2 = 6-氨基-3-甲基-4-氮杂杂-3-烯-2-酮肟）紫外可见分光光度法测定的pH范围为4.50-7.00。 [Ni-IV（L-2）（2）]（2+）的还原涉及pH小于或等于6.0且高于此值的2 e（-）转移（一步）路径，它表明涉及以下两个阶段Ni-III作为中间体。然而，[Ni-IV（L-1）]（2+）的还原在整个研究的整个pH范围内都是双相的。反应速率显示出对外部添加的产物Ni-II配合物的显着依赖性。实验结果和计算出的离子对常数的低值表明，电子转移的模式可能是外球型的。（C）1998 Elsevier ScienceLtd。保留所有权利。 [参考：22]

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《Polyhedron: The International Journal for Inorganic and Organometallic Chemistry》 |1998年第14期|共7页
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Dutta A.; Banerjee P.; Bhattacharya S.;
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1. Electron transfer between nickel(IV) oxime-imine complexes and nitrite: kinetics and mechanism [J] . Dutta A., Banerjee P., Bhattacharya S. Polyhedron: The International Journal for Inorganic and Organometallic Chemistry . 1998,第13a14期

机译：肟肟亚胺镍与亚硝酸盐之间的电子转移：动力学和机理
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Electron transfer between nickel(IV) oxime-imine complexes and nitrite: kinetics and mechanism

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