化学
共轭酸
氧化还原
电子转移
氧化剂
配体(生物化学)
反应性(心理学)
质子
水溶液
药物化学
无机化学
化学计量学
联氨(抗抑郁剂)
质子耦合电子转移
光化学
物理化学
离子
有机化学
色谱法
生物化学
替代医学
量子力学
受体
病理
医学
物理
作者
Jhimli Bhattacharyya,Kabita Dutta,Subrata Mukhopadhyay
出处
期刊:Dalton Transactions
[Royal Society of Chemistry]
日期:2004-01-01
卷期号: (18): 2910-2910
被引量:21
摘要
[Fe2(mu-O)(phen)4(H2O)2]4+ (1), one of the simplest mu-oxo diiron(III) complexes, quantitatively oxidises hydrazine to dinitrogen and itself is reduced to two moles of ferroin, [Fe(phen)3]2+ in presence of excess phenanthroline. The weak dibasic acid, 1 (pKa1= 3.71 +/- 0.05 and pKa2= 5.28 +/- 0.10 at 25.0 degrees C, I= 1.0 mol dm(-3)(NaNO3)) and its conjugate bases, [Fe2(mu-O)(phen)4(H2O)(OH)]3+ (2) and [Fe2(mu-O)(phen)4(OH)2]2+ (3) are involved in the redox process with the reactivity order 1 > 2 > 3 whereas N2H4 and not N2H5+ was found to be reactive in the pH interval studied 3.45-5.60. Cyclic voltammetric studies indicate poor oxidizing capacity of the title substitution-labile diiron complex, yet it oxidizes N2H4 with a moderate rate--a proton coupled electron transfer (1e, 1H+) drags the energetically unfavourable reaction to completion. The rate retardation in D2O media is substantially higher at higher pH due to the increasing basicity of the oxo-ligand in the order 3 > 2 > 1. Marcus calculations result an unacceptably high one-electron self-exchange rate for the iron center indicating an inner-sphere nature of the electron-transfer.
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