pH-Dependent metal-based redox couples as models for proton-coupled electron transfer reactions

Slattery, Spencer J.; Blaho, Jean K.; Lehnes, Joseph; Goldsby, Kenneth A.

doi:10.1016/s0010-8545(98)00143-x

Cited by 58 publications

(91 citation statements)

References 54 publications

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“…Structures of Fe(2), Fe (3) and [FeH 3 (3)](ClO 4 ) 2 are reported here whereas that of Fe(1) was the result of earlier work in this laboratory. 23 Other iron structures of these ligands include an adduct of Fe (3) (1-3); however, they are mentioned here due to their importance in understanding the redox chemistry of the iron complexes of H 3 (1-3) and the spontaneous aerial reduction of iron(III) to iron(II) in the presence of H 3 (3).…”

Section: Introductionmentioning

confidence: 60%

“…The titration of [FeH 3 (3)](BPh 4 ) 2 with standardized NaOH is shown in Figure 3. As in the reaction with [FeH 3 (1)](ClO 4 ) 3 (Figure 2), there is a single rise in the plot of mV vs mole ratio; however, this is found at 2.08. The third proton may be removed during oxidation of the starting complex to Fe(3), as the following reaction illustrates.…”

Section: Synthesis Of Iron(iii) Neutrals Fe(1-3) By Oxidation Of [Fmentioning

confidence: 84%

“…The deprotonation of the iron(III) imidazole complexes appears to be a simple acid-base equilibrium. Titration of [FeH 3 (1)](ClO 4 ) 3 with standardized sodium hydroxide ( Figure 2) yields a single inflection in the mV vs mole ratio plot at ~2.8. Failure to observe individual steps in the titration indicates that under these conditions, the individual ionization constants differ by <4 orders of magnitude (for example, the triprotic citric acid with pK a 's of 3.13, 4.77, and 6.40 exhibits a single inflection, as well, under these same conditions and in water).…”

Section: Synthesis and Reactivitymentioning

confidence: 99%

“…36 Removal of these protons can also be achieved by column chromatography on alumina in methanol; the product is eluted as a dark blue band. Acidification of Fe(1) with aqueous hydrochloric acid reforms [FeH 3 (1)] 3+ , as described in the Experimental Section.…”

Section: Synthesis and Reactivitymentioning

confidence: 99%

“…23 Other iron structures of these ligands include an adduct of Fe (3) (1-3); however, they are mentioned here due to their importance in understanding the redox chemistry of the iron complexes of H 3 (1-3) and the spontaneous aerial reduction of iron(III) to iron(II) in the presence of H 3 (3).…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Proton Control of Oxidation and Spin State in a Series of Iron Tripodal Imidazole Complexes

Brewer¹,

Brewer²,

Luckett³

et al. 2004

Inorg. Chem.

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show abstract

Section: Introductionmentioning

confidence: 60%

Section: Synthesis Of Iron(iii) Neutrals Fe(1-3) By Oxidation Of [Fmentioning

confidence: 84%

Section: Synthesis and Reactivitymentioning

confidence: 99%

Section: Synthesis and Reactivitymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Proton Control of Oxidation and Spin State in a Series of Iron Tripodal Imidazole Complexes

Brewer¹,

Brewer²,

Luckett³

et al. 2004

Inorg. Chem.

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Proton‐Coupled Electron Transfer Reactions Catalysed by 3 d Metal Complexes

Siewert

2015

Chemistry A European J

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Proton-coupled electron transfer (PCET) reactions are essential for a wide range of natural energy-conversion reactions and recently, the impact of PCET pathways has been exploited in artificial systems, too. The Minireview highlights PCET reactions catalysed by first-row transition-metal complexes, with a focus on the water oxidation, the oxygen reduction, the hydrogen evolution, and the CO2 reduction reaction. Special attention will be paid to systems in which the impact of such pathways is deduced by comparison to systems with "electron-only"-transfer pathways.

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Dinuclear Complexes Formed by Hydrogen Bonds: Synthesis, Structure and Magnetic and Electrochemical Properties

Granelli

Downward

Huber

et al. 2017

Chemistry A European J

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The synthesis is reported of a series of homo- and hetero-dinuclear octahedral complexes of the ligand 1, 1,2-bis(1-methyl-benzimidazol-2-yl) ethanol, where the two metal centres are linked by hydrogen bonds between coordinated alcohols and coordinated alkoxides. Homonuclear divalent M M , mixed-valent M M and heteronuclear M M' species are prepared. The complexes have been characterised by X-ray crystallography and show unusually short O⋅⋅⋅O distances for the hydrogen bonds. Magnetic measurements show the hydrogen-bond bridges can lead to ferromagnetic or antiferromagnetic coupling. The electrochemistry of the dinuclear species is significantly different from the mononuclear systems: the latter show irreversible waves in cyclic voltammograms as a result of the need to couple proton and electron transfer. The dinuclear species, in contrast, show reversible waves, which are attributed to rapid intramolecular proton transfer facilitated by the hydrogen-bonded structure.

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pH-Dependent metal-based redox couples as models for proton-coupled electron transfer reactions

Cited by 58 publications

References 54 publications

Proton Control of Oxidation and Spin State in a Series of Iron Tripodal Imidazole Complexes

Proton Control of Oxidation and Spin State in a Series of Iron Tripodal Imidazole Complexes

Proton‐Coupled Electron Transfer Reactions Catalysed by 3 d Metal Complexes

Dinuclear Complexes Formed by Hydrogen Bonds: Synthesis, Structure and Magnetic and Electrochemical Properties

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