NDLI: Unraveling the Mechanism of Water Oxidation Catalyzed by Nonheme Iron Complexes

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Unraveling the Mechanism of Water Oxidation Catalyzed by Nonheme Iron Complexes

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Codolà, Zoel Costas, Miquel Lloret-fillol, Julio Acuña-parés, Ferran Luis, Josep M.
Description	Author Affiliation: Acuña-Parés F ( Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus Montilivi, 17071, Girona (Spain).)
Abstract	Density functional theory (DFT) is employed to: 1) propose a viable catalytic cycle consistent with our experimental results for the mechanism of chemically driven $(Ce^{IV})$ $O_{2}$ generation from water, mediated by nonheme iron complexes; and 2) to unravel the role of the ligand on the nonheme iron catalyst in the water oxidation reaction activity. To this end, the key features of the water oxidation catalytic cycle for the highly active complexes $[Fe(OTf)_{2}(Pytacn)]$ (Pytacn: 1-(2′-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane; OTf: $CF_{3}SO_{3}^{})$ (1) and $[Fe(OTf)_{2}(mep)]$ (mep: N,N′-bis(2-pyridylmethyl)-N,N′-dimethyl ethane-1,2-diamine) (2) as well as for the catalytically inactive $[Fe(OTf)_{2}(tmc)]$ (tmc: N,N′,N′′,N′′′-tetramethylcyclam) (3) and $[Fe(NCCH_{3})(^{Me}Py_{2}CH-tacn)](OTf)_{2}$ $(^{Me}Py_{2}CH-tacn:$ N-(dipyridin-2-yl)methyl)-N′,N′′-dimethyl-1,4,7-triazacyclononane) (4) were analyzed. The DFT computed catalytic cycle establishes that the resting state under catalytic conditions is a $[Fe^{IV}(O)(OH_{2})(LN_{4})]^{2+}$ species (in which $LN_{4}=Pytacn$ or mep) and the rate-determining step is the OO bond-formation event. This is nicely supported by the remarkable agreement between the experimental $(ΔG^{≠}=17.6±1.6 kcal mol^{−1})$ and theoretical $(ΔG^{≠}=18.9 kcal mol^{−1})$ activation parameters obtained for complex 1. The OO bond formation is performed by an iron(V) intermediate $[Fe^{V}(O)(OH)(LN_{4})]^{2+}$ containing a $cis-Fe^{V}(O)(OH)$ unit. Under catalytic conditions $(Ce^{IV},$ pH 0.8) the high oxidation state $Fe^{V}$ is only thermodynamically accessible through a proton-coupled electron-transfer (PCET) process from the $cis-[Fe^{IV}(O)(OH_{2})(LN_{4})]^{2+}$ resting state. Formation of the $[Fe^{V}(O)(LN_{4})]^{3+}$ species is thermodynamically inaccessible for complexes 3 and 4. Our results also show that the cis-labile coordinative sites in iron complexes have a beneficial key role in the OO bond-formation process. This is due to the cis-OH ligand in the $cis-Fe^{V}(O)(OH)$ intermediate that can act as internal base, accepting a proton concomitant to the OO bond-formation reaction. Interplay between redox potentials to achieve the high oxidation state $(Fe^{V}O)$ and the activation energy barrier for the following OO bond formation appears to be feasible through manipulation of the coordination environment of the iron site. This control may have a crucial role in the future development of water oxidation catalysts based on iron.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	19
Volume Number	20
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2014-05-05
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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