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Issue 33, 2014
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Mechanism of water oxidation by non-heme iron catalysts when driven with sodium periodate

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Abstract

Iron tris(2-methylpyridyl)amine (TPA) and iron 1-(bis(2-methylpyridyl)amino)-2-methyl-2-propanoate (BPyA) salts are characterized as water oxidation catalysts (WOCs) using sodium periodate. Under the conditions used, these complexes serve as homogeneous WOCs as demonstrated via kinetic analysis and dynamic light scattering (DLS). The Fe(BPyA) salt serves as both a mononuclear and dinuclear catalyst, with the mononuclear form showing higher catalytic activity. Based on the H/D kinetic isotope effect and pH dependence, the rate determining step (RDS) in water oxidation (WO) by Fe(BPyA) is nucleophilic attack by water during O–O bond formation. In contrast, Fe(TPA) shows complex kinetic behavior due to the formation of multiple oxidation states of the complex in solution, each of which exhibits catalytic activity for WO. The RDS in WO by Fe(TPA) follows an equilibrium established between monomeric and dimeric forms of the catalyst. Under acidic conditions formation of the monomer is favored, which leads to an increase in the WO rate.

Graphical abstract: Mechanism of water oxidation by non-heme iron catalysts when driven with sodium periodate

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Article information


Submitted
23 Apr 2014
Accepted
27 Jun 2014
First published
01 Jul 2014

Dalton Trans., 2014,43, 12501-12513
Article type
Paper
Author version available

Mechanism of water oxidation by non-heme iron catalysts when driven with sodium periodate

A. R. Parent, T. Nakazono, S. Lin, S. Utsunomiya and K. Sakai, Dalton Trans., 2014, 43, 12501
DOI: 10.1039/C4DT01188K

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