A Fluorescence‐Based Screening Protocol for the Identification of Water Oxidation Catalysts

Detz, Remko J.; Abiri, Zohar; Kluwer, Alexander M.; Reek, Joost N. H.

doi:10.1002/cssc.201501193

Cited by 1 publication

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References 21 publications

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“…In addition, iron complexes where the methyl groups of the mcp ligand are replaced by protons or with the two pyridyl positions oxidized are also catalytically incompetent. 18 Therefore, the initial O2 evolution should came from the intact species before degradation. Altogether strongly indicates the molecularity of the catalytic system and that the original molecular complex is the active species.…”

Section: Manometry and Gc-ms On-line Studies Of The Gases Evolved In mentioning

confidence: 99%

Design of Iron Coordination Complexes as Highly Active Homogenous Water Oxidation Catalysts by Deuteration of Oxidation-Sensitive Sites

et al. 2018

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The nature of the oxidizing species in water oxidation reactions with chemical oxidants catalyzed by α-[Fe(OTf)2(mcp)] (mcp = N, N′-dimethyl-N,N′-bis(pyridin-2-ylmethyl)cyclohexane-1,2-diamine, OTf = trifluoromethanesulfonate anion), (1α) and β-[Fe(OTf)2(mcp)], (1β) has been investigated. Mössbauer spectroscopy provides definitive evidence that 1α and 1β generate oxoiron(IV) species as the resting state. Decomposition paths of the catalysts have been investigated by identifying and quantifying ligand fragments that form upon degradation. This analysis correlates the water oxidation activity of 1α and 1β with stability against oxidative damage of the ligand via aliphatic C-H oxidation. The site of degradation and the relative stability against oxidative degradation is shown to be dependent on the topology of the catalyst. Furthermore, the mechanisms of catalyst degradation have been rationalized by computational analyses, which also explain why the topology of the catalyst enforces different oxidation sensitive sites. This information has served for creating catalysts where sensitive C-H bonds have been replaced by C-D bonds. Deuterated analogs, D4-α-[Fe(OTf)2(mcp)] (D4-1α), D4-β-[Fe(OTf)2(mcp)] (D4-1β) and D6-β-[Fe(OTf)2(mcp)] (D6-1β) were prepared, and their catalytic activity has been studied. D4-1α proves to be an extraordinarily active and efficient catalyst (up to 91% of O2 yield); it exhibits initial reaction rates identical to its protio analogue, but it is substantially more robust towards oxidative degradation and yields more than 3400 TON (n(O2)/n(Fe)). Altogether evidence that the water oxidation catalytic activity is performed by a well-defined coordination complex and not by iron oxides formed after oxidative degradation of the ligands.

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Section: Manometry and Gc-ms On-line Studies Of The Gases Evolved In mentioning

confidence: 99%

Design of Iron Coordination Complexes as Highly Active Homogenous Water Oxidation Catalysts by Deuteration of Oxidation-Sensitive Sites

et al. 2018

View full text Add to dashboard Cite

show abstract

A Fluorescence‐Based Screening Protocol for the Identification of Water Oxidation Catalysts

Cited by 1 publication

References 21 publications

Design of Iron Coordination Complexes as Highly Active Homogenous Water Oxidation Catalysts by Deuteration of Oxidation-Sensitive Sites

Design of Iron Coordination Complexes as Highly Active Homogenous Water Oxidation Catalysts by Deuteration of Oxidation-Sensitive Sites

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