Measurement of Redox Reaction Volumes for Iron(III/II) Complexes Using High-Pressure Cyclic Staircase Voltammetry. Half-Cell Contributions to Redox Reaction Volumes

Sachinidis, John; Shalders, Richard D.; Tregloan, Peter A.

doi:10.1021/ic00104a031

Cited by 57 publications

(93 citation statements)

References 7 publications

(7 reference statements)

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“…The cis coordinated macrocycle, with its folded conformation, is better able to accommodate expansion of the cobalt ion upon reduction than the trans configuration, where the macrocycle encircles the metal and more effectively restricts coordinate bond expansion. This effect was seen previously during a study of the outer-sphere reduction of the isomeric cis-and trans-[CoL 14 Fig. 7.…”

Section: 37supporting

confidence: 75%

Pressure and temperature effects on metal-to-metal charge transfer in cyano-bridged Co^III–Fe^IIcomplexes

et al. 2005

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The effects of pressure and temperature on the energy (E op ) of the metal-to-metal charge transfer ( (where L 14 = 6-methyl-1,4,8,11-tetraazacyclotetradecan-6-amine) were examined. The changes in the redox potentials of the cobalt and iron metal centres with pressure and temperature were also examined and the results interpreted with Marcus-Hush theory. The observed redox reaction volumes can mainly be accounted for in terms of localised electrostriction effects. The shifts in E op due to both pressure and temperature were found to be less than the shifts in the energy difference (

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Section: 37supporting

confidence: 75%

Pressure and temperature effects on metal-to-metal charge transfer in cyano-bridged Co^III–Fe^IIcomplexes

et al. 2005

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“…From these tables it can be seen that, despite the difficulty of obtaining reproducible electrochemical results from pressurized systems (see introduction), a general good agreement between the data reported by different authors is found. Furthermore, several studies for the ferri/ferrocyanide couple have been undertaken [37,52,53] in different electrolytes showing that for this couple the DV complex (complex-ion reduction volume) is almost independent of the nature or concentration of the electrolyte.…”

Section: Theorymentioning

confidence: 99%

“…The estimated intrinsic and electrostrictive contributions for a range of couples were studied in aqueous solutions [37,53,54,81] and are summarized in Table 3. It can be seen that the electrostrictive volume change is around 20 cm 3 mol…”

Section: Pressure Effects On the Redox Potential Of Metal Complexesmentioning

confidence: 99%

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Electrochemistry at High Pressures: A Review

2004

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High pressure electrochemical studies are potentially dangerous and less immediately implemented than conventional investigations. Technical obstacles related to properties of the working electrode material, preparation of its surface, availability of suitable reference electrodes, and the need for specially designed high pressure equipment and cells may account for the relative lack of experimental data on electrochemistry at high pressures. However, despite the stringent requirements for system and equipment stability, significant developments have been made in recent years and the combination of electrochemical methods with high hydrostatic pressure has provided useful insights into the thermodynamics, kinetics, and other physico-chemical characteristics of a wide range of redox reactions. In addition to fundamental information, high pressure electrochemistry has also lead to a better understanding of a variety of processes under non-classical conditions with potential applications in today×s industrial environment from extraction and electrosynthesis in supercritical fluids to measurement of the pH at the bottom of the ocean. The purpose of this article is to detail the experimental pressurizing apparatus for electroanalytical measurements at high pressures and to review the relevant literature on the effect of pressure on electrode processes and on the properties of aqueous electrolyte solutions.

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“…Previous studies have discussed the correlation between electrostrictive changes ∆V elec and ∆z 2 /r {∆z 2 ϭ (z ox ) 2 Ϫ (z red ) 2 ; r ϭ radius of species}. [24] Calculated van der Waal's volumes for the mono-, di-, and trinuclear complexes {[Ru(phen) 2 (HAT)] nϩ , [{Ru(phen) 2 } 2 (µ-HAT)] nϩ , and [{Ru(phen) 2 } 2 (µ-HAT)] nϩ } were 518, 847, and 1177 Å 3 , respectively: even allowing for the approximation incurred because of the non-spherical nature of the di-and trinuclear species, the constancy of ∆V complex cannot be accounted for by this simple ∆z 2 /r relationship.…”

Section: High-pressure Electrochemistrymentioning

confidence: 99%

Redox Characteristics and Anion Association Behaviour of Stereoisomeric Forms of Mono- and Oligonuclear Metal Complexes Using High Pressure Electrochemistry

Yeomans

Kelso

Tregloan

et al. 2001

Eur. J. Inorg. Chem.

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The effect of the presence of the anions PF 6 − , BF 4 − , ClO 4 − , and tosylate − on the potentials of the Ru III/II redox processes in a series of mono-, di-, and trinuclear complexes involving polypyridyl ligands are reported. The anions gives rise to a cathodic shift in the respective redox potentials in the sequence PF 6 − Ͻ BF 4 − ഠ ClO 4 − Ͻ tos − , with the magnitude of the shifts being largest for the tri-nuclear and smallest for the mononuclear species. In one dinuclear complex, a variation of anion was also observed to affect the difference in potentials between the [6+/5+] and [5+/4+] couples. These effects

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Measurement of Redox Reaction Volumes for Iron(III/II) Complexes Using High-Pressure Cyclic Staircase Voltammetry. Half-Cell Contributions to Redox Reaction Volumes

Cited by 57 publications

References 7 publications

Pressure and temperature effects on metal-to-metal charge transfer in cyano-bridged Co^III–Fe^IIcomplexes

Pressure and temperature effects on metal-to-metal charge transfer in cyano-bridged Co^III–Fe^IIcomplexes

Electrochemistry at High Pressures: A Review

Redox Characteristics and Anion Association Behaviour of Stereoisomeric Forms of Mono- and Oligonuclear Metal Complexes Using High Pressure Electrochemistry

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Measurement of Redox Reaction Volumes for Iron(III/II) Complexes Using High-Pressure Cyclic Staircase Voltammetry. Half-Cell Contributions to Redox Reaction Volumes

Cited by 57 publications

References 7 publications

Pressure and temperature effects on metal-to-metal charge transfer in cyano-bridged CoIII–FeIIcomplexes

Pressure and temperature effects on metal-to-metal charge transfer in cyano-bridged CoIII–FeIIcomplexes

Electrochemistry at High Pressures: A Review

Redox Characteristics and Anion Association Behaviour of Stereoisomeric Forms of Mono- and Oligonuclear Metal Complexes Using High Pressure Electrochemistry

Contact Info

Product

Resources

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Pressure and temperature effects on metal-to-metal charge transfer in cyano-bridged Co^III–Fe^IIcomplexes

Pressure and temperature effects on metal-to-metal charge transfer in cyano-bridged Co^III–Fe^IIcomplexes