Mechanistic studies on oxidation of hydrazine by a mu-oxo diiron(III,III) complex in aqueous acidic media-proton coupled electron transfer

Dalton Transactions : an International Journal of Inorganic Chemistry
Jhimli BhattacharyyaSubrata Mukhopadhyay

Abstract

[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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Citations

Nov 26, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Suranjana DasSubrata Mukhopadhyay
May 31, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Suranjana Das, Subrata Mukhopadhyay
Jul 10, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Ritu MishraRupendranath Banerjee
Mar 14, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Jhimli BhattacharyyaSubrata Mukhopadhyay
Aug 19, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Pulak Chandra MandalSubrata Mukhopadhyay
Apr 27, 2011·The Journal of Physical Chemistry. a·Maharudra ChakrabortySubrata Mukhopadhyay

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