Entropic and enthalpic contributions to the solvent dependence of the thermodynamics of transition-metal redox couples

Sahami, Saeed; Weaver, Michael J.

doi:10.1016/s0022-0728(81)80147-7

Cited by 111 publications

(98 citation statements)

References 33 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The 5S~ values listed in the last column of Table I are obtained from Eq. Similar breakdowns of the dielectric continuum model in predicting reaction entropies have been found for several bulk solution couples in a number of solvents (1)(2)(3)(4)(5). There is clearly no general pattern of agreement between the experimental and these calculated quantities, the Born treatment predicting a much milder solvent dependence of AS~ than is observed.…”

Section: Reactant-solvent Interactionssupporting

confidence: 56%

“…Indeed, we have recently obtained such a result for a specifically adsorbed Co (III)/(II) sepulchrate couple vs. the corresponding bulk solution couple (7). However, in actuality even ~S~ for an outer-sphere reaction might be expected to differ significantly from hS~ in a given solvent medium, bearing in mind the structure sensitivity of ionic entropies (1)(2)(3)(4)(5) and the possibility that the solvating environment in the vicinity of the surface may differ significantly from that in the bulk solution. However, in actuality even ~S~ for an outer-sphere reaction might be expected to differ significantly from hS~ in a given solvent medium, bearing in mind the structure sensitivity of ionic entropies (1)(2)(3)(4)(5) and the possibility that the solvating environment in the vicinity of the surface may differ significantly from that in the bulk solution.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Utility of Surface Reaction Entropies for Examining Reactant‐Solvent Interactions at Electrochemical Interfaces. Ferricinium‐Ferrocene Attached to Platinum Electrodes

Hupp

Weaver

1984

J. Electrochem. Soc.

Self Cite

View full text Add to dashboard Cite

show abstract

Section: Reactant-solvent Interactionssupporting

confidence: 56%

mentioning

confidence: 99%

Utility of Surface Reaction Entropies for Examining Reactant‐Solvent Interactions at Electrochemical Interfaces. Ferricinium‐Ferrocene Attached to Platinum Electrodes

Hupp

Weaver

1984

J. Electrochem. Soc.

Self Cite

View full text Add to dashboard Cite

show abstract

“…48 An L-shaped electrode (disk oriented vertically) was used for the CV measurements and ECL experiments. The working electrode was polished prior to every experiment with 0.3 μm alumina particles dispersed in water, followed by sonication in ethanol and water for several minutes.…”

Section: Methodsmentioning

confidence: 99%

Synthesis, Electrochemistry, and Electrogenerated Chemiluminescence of Two BODIPY-Appended Bipyridine Homologues

Teesdale

Pupillo

et al. 2013

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Two new 2,2’-bipyridine (bpy) derivatives containing ancillary BODIPY chromophores attached at the 5- and 5’-positions (BB3) or 6- and 6’-positions (BB4) were prepared and characterized. In this work, the basic photophysics, electrochemistry and electrogenerated chemiluminescence (ECL) of BB3 and BB4 are compared with those previously reported for a related bpy-BODIPY derivative (BB2) (J. Phys. Chem. C 2011, 115, 17993–18001). Cyclic voltammetry revealed that BB3 and BB4 display reversible 2e− oxidation and reduction waves, which consist of two closely spaced (50 – 70 mV) 1e− events. This redox behavior is consistent with the frontier molecular orbitals calculated for BB3 and BB4 and indicates that the 2,2’-bipyridine spacer of each bpy- BODIPY homologue does not facilitate efficient electronic communication between the tethered indacene units. In the presence of a coreactant such as tri-n-propylamine (TPA) or benzoyl peroxide (BPO), BB3 and BB4 exhibit strong ECL and produce spectra that are very similar to their corresponding photoluminescence profiles. The ECL signal obtained under annihilation conditions, however, is significantly different and is characterized by two distinct bands. One of these bands is centered at ~570 nm and is attributed to emission via an S- or T-route. The second band, occurs at longer wavelengths and is centered around ~740 nm. The shape and concentration dependence of this long-wavelength ECL signal is not indicative of emission from an excimer or aggregate, but rather is suggests that a new emissive species is formed from the bpy-BODIPY luminophores during the annihilation process.

show abstract

“…The entropy of the [Fe(Hdmg)2(~im)2]+'0 redox couple was obtained as 71 J mol-I K-from careful measurements of ElI2 at several temperatures. The corresponding value for the [~u@hen)31~+'~+ complex was 92 J mol-I K-', at I = 0.10 M KC1 (28). From these data we calculated the activation parameters shown in Table 1.…”

Section: ) -mentioning

confidence: 99%

Electron transfer and autoxidation kinetics of the bis(imidazole)bis(dimethylglyoximato)iron(II) complex

Toma¹,

Silva²

1986

Can. J. Chem.

View full text Add to dashboard Cite

. Can. J. Chem. 64, 1280Chem. 64, (1986. The properties and reactivity of the bis(imidazo1e)bis-(dimethylglyoximato)irn(II) complex have been studied based on spectroelectrochemistry, cyclic voltammetry, and stopped-flow kinetics in aqueous solution. The autoxidation reaction was found to be inhibited by the imidazole ligand in excess but susceptible to copper(I1) catalysis. In this case a mechanism has been proposed, consisting of a rapid electron transfer followed by the reoxidation of the resulting Cu(1) species by 02. HENRIQUE E. TOMA et ANTONIO CARLOS C. SILVA. Can. J. Chem. 64, 1280Chem. 64, (1986.OpCrant en solution aqueuse et faisant appel i la spectroClectrochirnie, i la voltarnktrie cyclique et i la cinCtique par flux stoppC, on a CtudiC les propriCtCs et la rCactivitC du complexe bis(imidazo1e) bis(dimCthyg1yoximato) fer(I1). On a trouvC que la rCaction d'auto-oxydation est inhibCe par le ligand irnidazole qui est 1jrCsent en excks, alors qu'elle est susceptible i la catalyse par le cuivre(I1). Dans ce cas, on propose un mCcanisme d'aprks lequel il se produit une transfert rapide d'Clectron qui est suivi d'une rkoxydation, par le 0 2 , de l'espkce Cu(1) qui rCsulte.[Traduit par la revue]. IntroductionDioxime complexes of iron(II) are interesting examples of coordination compounds which mimic hemoglobin and mioglobin in their ability t o reversibly bind carbon monoxide (1-4).Among the several dioxime complexes, the bis(dimethylg1y-oximato)bis(irnidazole)iron(II) complex [Fe(Hdmg)2(Him)J, because of its well known molecular structure (5) which resembles the porphyrin species with biologically important ligands, has attracted our attention. O n the other hand, in contrast with the pyridine analogues, the imidazole complex is soluble enough in water for comparative studies with the biological hemes. In this work we have studied the properties and reactivity of the [Fe(Hdmg)2(Him)2] complex, with particular emphasis o n the electrochemistry and redox kinetics in aqueous solution. We have also investigated the autoxidation mechanisms, including the copper-catalyzed reaction, because of their possible relevance to the understanding of the biological oxidation processes (6)(7)(8). Experimental The electronic spectra of the complexes in the visible and uv region were recorded on a Cary 17 or a Hewlett-Packard 8451 diode-may spectrophotometer fittedwith thermostatted cell compartments. Cyclic voltammetry measurements were carried out with a Princeton Applied Research instrument, consisting of a 173 potentiostat and a 175 universal programmer. A platinum electrode was employed for the measurements, using the conventional Luggin capillary with the Ag/AgC1(1 M KCl) reference electrode in a non-isothermic mangement. A platinum wire was used as the auxiliary electrode.Spectroelectrochemica1 measurements were carried out using the diode-may spectrophotometer and the 173 potentiostat, with a transparent electrochemical cell of 0.03 cm internal optical pathlength. A gold minigrid was employed as the working electro...

show abstract

Entropic and enthalpic contributions to the solvent dependence of the thermodynamics of transition-metal redox couples

Cited by 111 publications

References 33 publications

Utility of Surface Reaction Entropies for Examining Reactant‐Solvent Interactions at Electrochemical Interfaces. Ferricinium‐Ferrocene Attached to Platinum Electrodes

Utility of Surface Reaction Entropies for Examining Reactant‐Solvent Interactions at Electrochemical Interfaces. Ferricinium‐Ferrocene Attached to Platinum Electrodes

Synthesis, Electrochemistry, and Electrogenerated Chemiluminescence of Two BODIPY-Appended Bipyridine Homologues

Electron transfer and autoxidation kinetics of the bis(imidazole)bis(dimethylglyoximato)iron(II) complex

Contact Info

Product

Resources

About