Formal Reduction Potential Research Articles

Probing the Molecular Interactions of Electrochemically Reduced Vitamin B2 with CO2.

The electrochemical reduction of riboflavin (vitamin B2) in a dimethyl sulfoxide solvent was examined under a CO2 atmosphere and compared with results under an argon atmosphere. Variable-scan-rate cyclic voltammetry combined with controlled potential electrolysis (CPE) and analysis by UV-vis and EPR spectroscopies provided insights into the nature of interactions of reduced flavins with dissolved CO2. Reductive exhaustive CPE experiments under CO2 indicated an overall two-electron stoichiometry, compared to one-electron reduction under an argon atmosphere, due to the lowering of the formal one-electron reduction potential of the flavin radical anion to form the dianion, which can be rationalized by riboflavin-CO2 molecular interactions. UV-vis spectroscopic measurements confirmed complete chemical reversibility of the redox transformations over extended time scales. Digital simulation modeling of the voltammetric data enabled extraction of thermodynamic and kinetic parameters for the proposed mechanism, comprising multiple proton-coupled electron transfer steps, diamagnetic anions, radical anions, and neutral radical intermediates enroute to the fully reduced state, as well as evidence of a long-lived solution phase complex of the reduced riboflavin with CO2.

Electrokinetics of Nitrite to Ammonia Conversion in the Neutral Medium Over A Platinum Surface.

Polycrystalline Pt electrode was employed to selectively convert nitrite ions ( ) into useful nitrogenous compound through electrochemical reduction reaction in neutral medium. According to adsorptive stripping analysis, the reduction process produced nitric oxide (NO) on the surface of Pt electrode. The spectroscopic test and gas chromatographic studies discovered the presence of ammonia (NH3) in the electrolyzed solution, suggesting the transformation of adsorbed NO into NH3 during the reverse scan. Scan rate dependent investigation was performed to elucidate kinetic information relating to this reaction on Pt surface. From Ep vs scan rate (υ) and jp vs υ (logarithmic plot), it was found that the conversion of ion into NO is an irreversible reaction which relies on the diffusion of ions to electrode surface. The Tafel analysis unveiled that the first electron transfer sets the overall reaction rate, having formal reduction potential, E0'=-0.46 V and standard heterogeneous rate constant, k0= cm s-1. Reductive transfer coefficient (α) is another kinetics parameter, which was found to be approximate 0.77 from the difference between Ep and Ep/2 of the voltammograms obtained over scan rate range 0.005 V s-1 to 0.250 V s-1, indicating a stepwise process. According to temperature-dependent voltammograms, the nitrite reduction reaction on Pt had a calculated activation energy of about 19.8 kJ mol-1 and a pre-exponential factor of about 8.39×103 mA cm-2.

Electrochemical behavior and electromotive force measurements of U3+/U0 in molten MgCl2-NaCl

The electrochemical behavior of UCl3 was investigated in molten MgCl2NaCl at 550 °C. Using electromotive force measurements, we have measured the formal reduction potential (Eo’) at 550 °C of U3+/U0 as +0.276 V vs. Mg/MgCl2 (-1.400 V vs. Ag/AgCl 5 mol%) on the molal scale. We also present the design and construction of a sealed Mg/MgCl2 reference electrode and have determined this system demonstrates ideal nonpolarizable electrode behavior, confirming it as an appropriate choice of reference electrode in molten chloride salts.

Combined Effects of Hemicolligation and Ion Pairing on Reduction Potentials of Biphenyl Radical Cations.

Formal reduction potentials of highly oxidizing and short-lived radical cations of substituted biphenyls generated by pulse radiolysis in 1,2-dichloroethane (DCE) were measured using a redox equilibrium ladder method. The effect of halide ion-radical interactions on reduction potentials of biphenyls was examined by utilizing the ability of DCE to release Cl- in the vicinity of the radical cation. The Hammett correlation of measured potentials across a range of over 700 mV shows saturation at high Hammett sigma values. This effect has been explained by both ion-pairing and hemicolligation interactions between biphenyl radical cations and Cl- and appears to modulate reduction potentials by as much as 400 mV. This finding offers a convenient way to manipulate the energetics of electron transfer involving organic redox species.

Intramolecular Hydrogen Bonding Effect on the Electron-Transfer Thermodynamics of a Series of o-Nitrobenzyl Alcohol Derivatives.

From thermoelectrochemical experiments and electronic structure calculations of a series of nitrobenzyl alcohol derivatives, the effect of intramolecular hydrogen bonding (IHB) on the electron transfer thermodynamics is discussed on a molecular basis. A linear correlation between formal reduction potential (E1/2) values and temperature was obtained for the temperature range from 300 to 350 K. Estimated electron transfer entropy values (ΔS)─determined from this dependence─and the enthalpy (ΔΔH) changes relative to o-nitrobenzyl alcohol confirmed that the effect of the formation of IHB proved to be decisive in the charge-transfer thermodynamics. The possibility of intermolecular hydrogen bonding is further discussed upon comparing thermodynamic data among three different solvents.

Incorporation of a molybdenum atom in a Rubredoxin-type Centre of a de novo-designed α3DIV-L21C three-helical bundle peptide

The rational design and functionalization of small, simple, and stable peptides scaffolds is an attractive avenue to mimic catalytic metal-centres of complex proteins, relevant for the design of metalloenzymes with environmental, biotechnological and health impacts. The de novo designed α3DIV-L21C framework has a rubredoxin-like metal binding site and was used in this work to incorporate a Mo-atom. Thermostability studies using differential scanning calorimetry showed an increase of 4 °C in the melting temperature of the Mo-α3DIV-L21C when compared to the apo-α3DIV-L21C. Circular dichroism in the visible and far-UV regions corroborated these results showing that Mo incorporation provides stability to the peptide even though there were almost no differences observed in the secondary structure. A formal reduction potential of ∼ −408 mV vs. NHE, pH 7.6 was determined. Combining electrochemical results, EPR and UV–visible data we discuss the oxidation state of the molybdenum centre in Mo-α3DIV-L21C and propose that is mainly in a Mo (VI) oxidation state.

Boosting the Selective Electrochemical Signals for Simultaneous Determination of Chloramphenicol and Furazolidone in Food Samples by Using ZnFe2O4-Based Sensing Platform: Correlation between Analyte Molecular Structure and Electronic Property of Electrode Materials

In this study, ZnFe2O4-based nanostructures, including ZnFe2O4 nanoparticles and ZnFe2O4/ZnO nanocomposite, were introduced on screen-printed electrodes surface (SPEs) for enhancing the selective electrochemical signals towards the chloramphenicol (CAP) and furazolidone (FZD) antibiotics. The difference in the molecular structure of CAP and FZD leads to significant changes in adsorption capacity and electron transfer kinetic at modified electrodes. Interestingly, FZD antibiotic with formal reduction potential (E0’) near the Fermi level of ZnFe2O4-based nanostructures showed a strong dependence of electrochemical response with electron transfer kinetic. In contrast, CAP antibiotic with E0’ away from the Fermi level of ZnFe2O4-based nanostructures showed the high sensitivity of electrochemical response with the electroactive surface area of modified electrodes. The obtained results might offer the basis to develop a suitable approach for improving the analytical performance of advanced spinel oxide nanostructures-based electrochemical sensing devices. Under optimal conditions, ZnFe2O4/ZnO/SPEs enabled the simultaneous monitoring of CAP and FZD in the linear working ranges of 0.5–100 μM and 0.5–75 μM with high electrochemical sensitivity of 1.87 and 1.82 μA μM−1 cm−2, respectively. The ZnFe2O4-based electrochemical nanosensor exhibited high repeatability and long-term storage stability for simultaneous analysis of CAP and FZD in milk sample.

Resolving Halide Ion Stabilization through Kinetically Competitive Electron Transfers.

Stabilization of ions and radicals often determines reaction kinetics and thermodynamics, but experimental determination of the stabilization magnitude remains difficult, especially when the species is short-lived. Herein, a competitive kinetic approach to quantify the stabilization of a halide ion toward oxidation imparted by specific stabilizing groups relative to a solvated halide ion is reported. This approach provides the increase in the formal reduction potential, ΔE°′(Χ•/–), where X = Br and I, that results from the noncovalent interaction with stabilizing groups. The [Ir(dF-(CF3)-ppy)2(tmam)]3+ photocatalyst features a dicationic ligand tmam [4,4′-bis[(trimethylamino)methyl]-2,2′-bipyridine]2+ that is shown by 1H NMR spectroscopy to associate a single halide ion, Keq = 7 × 104 M–1 (Br–) and Keq = 1 × 104 M–1 (I–). Light excitation of the photocatalyst in halide-containing acetonitrile solutions results in competitive quenching by the stabilized halide and the more easily oxidized diffusing halide ion. Marcus theory is used to relate the rate constants to the electron-transfer driving forces for oxidation of the stabilized and unstabilized halide, the difference of which provides the increase in reduction potentials of ΔE°′(Br•/–) = 150 ± 24 meV and ΔE°′(I•/–) = 67 ± 13 meV. The data reveal that Keq is a poor indicator of these reduction potential shifts. Furthermore, the historic and widely used assumption that Coulombic interactions alone are responsible for stabilization must be reconsidered, at least for polarizable halogens.

Low Voltage Voltammetry Probes Proton Dissociation Equilibria of Amino Acids and Peptides

Platinum-catalyzed electrochemical reduction of dissociable protons at low potentials was used to investigate proton dissociation equilibria of freely diffusing and peptide-incorporated charged amino acids. We first demonstrate with five charged essential amino acids and their analogs that the electrochemically induced deprotonation of each amino acid occurs at distinct formal reduction potential. Moreover, the observed direct reduction for all the charged species, excluding arginine, occurs at low potentials suitable for investigation under aqueous conditions (-0.4 to -0.9 V vs Ag/AgCl). The direct proton reduction was resolved via deconvolution of the observed differential pulse voltammogram (DPV) from background hydronium reduction and water electrolysis. A linear correlation was found between the formal reduction potentials and the pKa values of the dissociable protons hosted by various molecular moieties in the amino acids and their analogs and further verified with tripeptides. DPV of poly(l-lysine) decamer (Lys10) distinctively resolved the pKa values of the amino groups in the side chains and N-terminus, at a resolution not possible by conventional acid-base titration. This work demonstrates selective electrochemical titration of dissociable protons in charged amino acids in the free state and as residues in biomolecules, as well as the utility of DPV to indirectly interrogate local electrostatic environments that are essential to the stability and function of biomolecules.

Electrochemical Triggering of Reflectin Protein Assembly

In this work, we demonstrate electrochemical triggering and assembly of reflectin, the protein that mediates neuronal fine-tuning of color reflected from skin cells used for camouflage and communication in squids. Electrochemical reduction of histidine residues in the protein acts as an in vitro surrogate for phosphorylation in vivo, driving the assembly previously shown to regulate its function. Using micro-drop voltammetry and in situ dynamic light scattering, we demonstrate selective reduction of the imidazolium sidechains of histidine in monomers, oligopeptides and reflectin in acidic solution. The formal reduction potential of imidazolium proves readily distinguishable from those of hydronium and primary amines, allowing unequivocal confirmation of the direct and energetically-selective deprotonation of histidine in reflectin. The resulting “electro-assembly” methodology provides a new approach to probe, understand, and control the mechanisms that dynamically tune protein structure and function. Figure 1

Solvometallurgical Recovery of Platinum Group Metals from Spent Automotive Catalysts

Extraction and separation of platinum group metals (PGMs) from secondary raw materials are usually carried out via hydrometallurgical processes. These processes use strongly oxidizing acidic solutions, such as aqua regia or hydrochloric acid in the presence of chlorine gas, which may have negative environmental impacts and are dangerous. In this paper, a solvometallurgical approach was developed for the sustainable recovery of PGMs from spent automotive exhaust catalysts. The PGMs were leached using FeCl3 or CuCl2 as oxidizing agents in the organic solvents dimethyl sulfoxide (DMSO) or acetonitrile (CH3CN). Palladium was quantitatively dissolved in CuCl2/CH3CN, CuCl2/DMSO, and FeCl3/DMSO with only 10–20% codissolution of Pt and Rh. By adjusting the concentration of the oxidizing agent in CH3CN, Pd was selectively leached with 0.01 mol L–1 FeCl3, whereas Pt and Rh could be dissolved in a more concentrated FeCl3 solution (0.3 mol L–1). The solvoleaching of PGMs was investigated in depth by UV–vis spectra and electrochemical properties (i.e., cyclic voltammograms and formal reduction potentials of the Fe3+/Fe2+ and Cu2+/Cu+ couples in DMSO and CH3CN). After leaching, CH3CN was easily recovered by distillation. The Pd-containing residue was dissolved in water, from which Pd sponge was produced by reduction with formic acid. Meanwhile, the residue containing the solid chloride salts of Fe(III), Pt(IV), and Rh(III) was redissolved in ethylene glycol or DMSO for further purification by nonaqueous solvent extraction (NASX). The ionic liquid Aliquat 336 diluted in p-cymene showed selective extraction of Fe(III) and Pt(IV) while leaving Rh(III) in the raffinate. The loaded ionic liquid was recycled after selective stripping of Fe(III) with water and Pt(IV) with a thiourea solution. A flow sheet comprising solvoleaching and NASX is proposed. The closed-loop solvoleaching of PGMs with less-hazardous chemicals (FeCl3/CH3CN) avoids the emission of toxic or flammable gases (Cl2, H2, and NOx) while reducing the consumption of acids and bases and limiting the generation of waste water. In addition, NASX with an ionic liquid may be a more sustainable alternative for the conventional separation of PGMs.

Electrochemistry as a surrogate for protein phosphorylation: voltage-controlled assembly of reflectin A1.

Phosphorylation is among the most widely distributed mechanisms regulating the tunable structure and function of proteins in response to neuronal, hormonal and environmental signals. We demonstrate here that the low-voltage electrochemical reduction of histidine residues in reflectin A1, a protein that mediates the neuronal fine-tuning of colour reflected from skin cells for camouflage and communication in squids, acts as an in vitro surrogate for phosphorylation in vivo, driving the assembly previously shown to regulate its function. Using micro-drop voltammetry and a newly designed electrochemical cell integrated with an instrument measuring dynamic light scattering, we demonstrate selective reduction of the imidazolium side chains of histidine in monomers, oligopeptides and this complex protein in solution. The formal reduction potential of imidazolium proves readily distinguishable from those of hydronium and primary amines, allowing unequivocal confirmation of the direct and energetically selective deprotonation of histidine in the protein. The resulting 'electro-assembly' provides a new approach to probe, understand, and control the mechanisms that dynamically tune protein structure and function in normal physiology and disease. With its abilities to serve as a surrogate for phosphorylation and other mechanisms of charge neutralization, and to potentially isolate early intermediates in protein assembly, this method may be useful for analysing never-before-seen early intermediates in the phosphorylation-driven assembly of other proteins in normal physiology and disease.

Predicting Properties of Iron(III) TAML Activators of Peroxides from Their III/IV and IV/V Reduction Potentials or a Lost Battle to Peroxidase.

A cyclic voltammetry study of a series of iron(III) TAML activators of peroxides of several generations in acetonitrile as solvent reveals reversible or quasireversible FeIII/IV and FeIV/V anodic transitions, the formal reduction potentials (E°') for which are observed in the ranges 0.4-1.2 and 1.4-1.6 V, respectively, versus Ag/AgCl. The slope of 0.33 for a linear E°'(IV/V) against E°'(III/IV) plot suggests that the TAML ligand system plays a bigger role in the FeIII/IV transition, whereas the second electron transfer is to a larger extent an iron-centered phenomenon. The reduction potentials appear to be a convenient tool for analysis of various properties of iron TAML activators in terms of linear free energy relationships (LFERs). The values of E°'(III/IV) and E°'(IV V-1 ) correlate 1) with the pKa values of the axial aqua ligand of iron(III) TAMLs with slopes of 0.28 and 0.06 V, respectively; 2) with the Stern-Volmer constants KSV for the quenching of fluorescence of propranolol, a micropollutant of broad concern; 3) with the calculated ionization potentials of FeIII and FeIV TAMLs; and 4) with rate constants kI and kII for the oxidation of the resting iron(III) TAML state by H2 O2 and reactions of the active forms of TAMLs formed with donors of electrons S, respectively. Interestingly, slopes of log kII versus E°'(III/IV) plots are lower for fast-to-oxidize S than for slow-to-oxidize S. The log kI versus E°'(III/IV) plot suggests that the manmade TAML catalyst can never be as reactive toward H2 O2 as a horseradish peroxidase enzyme.

Reprint of "Proton-coupled electron transfer from an interfacial phenol monolayer"

Abstract A tert-butyl protected phenol is covalently link to a mixed self-assembled monolayer on a gold or platinum electrode. The phenol reduction potential shows the expected pH-dependence of a one-electron, one-proton couple with a decrease in formal reduction potential of 59 ± 5 mV per pH. A titration of the phenol is observed with a pKa of 13.2 and the reduction potential for the phenolate is 0.11 V . NHE. The kinetic behavior of the proton-coupled oxidation deviates substantially from the commonly used models for a step-wise reaction that assume the proton transfer reactions are in equilibrium throughout the reaction. A novel model for step-wise proton-coupled reactions is presented that fully accounts for the pH dependent kinetics and allows the formal rate constants and the transfer coefficients to be determined.

Determination of HOMO and LUMO Level of Polythiophene, Poly(3-Thiophene Acetic Acid), Polypyrrole and Chlorophyll via Cyclic Voltammetry Method

Cyclic voltammetry can be used to investigate the chemical reactivity of species ion via oxidation and reduction process. The purpose of this study is to determine the level energy of high occupied molecule orbital (HOMO) and low unoccupied molecule orbital (LUMO) in polythiophene (PT), Poly (3-thiophene acetic acid) (P3TAA), polypyrrole (PPY) and chlorophyll (Chlo) through oxidation and reduction of molecular ions by cyclic voltammetry method. PT, P3TAA, PPY and Chlo solutions were prepared in a solvent of acetonitrile at the concentration range of 10-2 to 10-4 M. The current-voltage measurements for these solutions are performed using cyclic voltammetry method on input voltage from -2.0 V to 2.0 V. The working electrode used is indium tin oxide (ITO). The result of voltammogram is showed that the activity of PT species were produced three oxidation and one reduction processes. The formal reduction potential, Eo¢ is 0.83 (positive) meaning that oxidation process was dominant. So that the reaction of PT species was exhibited irreversible electrochemical behavior. The reaction of P3TAA species was exhibited reversible electrochemical behavior, where the range value of oxidation, DEpa and reduction, DEpc were in range of 0.825 V to 1.120 V and -0.230 V to 0.131 V respectively. PYY species reaction was exhibited irreversible electrochemical behavior where two oxidation states occur within -0.145 V to -0.202 V and 0.870 V to 1.63 V respectively. The species activity of Chlo was exhibited irreversible electrochemical behavior where only the oxidation process was obviously appeared at range of 0.80 V to 0.95 V. The LUMO energy levels of PT, P3TAA PPY and Chlo were 5.84 eV, 5.34 eV, 1.10 eV and 3.85 eV respectively, while HOMO energy levels of PT, P3TAA PPY and Chlo were 4.61 eV, 4.25eV, 3.70 eV and 5.93 eV. The average value of energy gap of PT, P3TAA, PPY and Chlo were 1.23 eV, 1.08 eV, 2.23 eV and 1.10 eV respectively.

Homogeneous electron-transfer reaction between anionic species of anthraquinone derivatives and molecular oxygen in acetonitrile solutions: Electrochemical properties of disperse red 60

In this work, the voltammetric behaviour of disperse red 60 (DR60) in acetonitrile solutions in the presence of water and dioxygen (O2) is reported for the first time. DR60 can be reduced in two one-electron steps to form first the anion radical and then the dianion. The first reduction process of DR60 is affected by the water content of the acetonitrile, with digital simulations of the cyclic voltammetric waves supporting interactions between the radical anion and water molecules. Additionally, the presence of O2 modifies the first voltammetric process of DR60, suggesting the occurrence of homogeneous electron transfer reaction between anion radicals of DR60 and O2. Furthermore, the water content of the acetonitrile also affects the reduction wave of O2, with digital simulations supporting the occurrence of two association steps with the superoxide intermediate. The homogeneous electron transfer reaction between the quinone and oxygen species was also examined by reacting bulk electrolyzed solutions containing the anions of DR60 and O2 with neutral species of O2 and DR60, respectively, and recording the variation in the colour of the electrolyzed solutions. An equilibrium constant value was obtained from the difference between the formal reduction potentials of DR60 and O2 (−0.9955 and −0.9770, respectively, both vs. Ag in CH3CN with 0.5 M n-Bu4NPF6), indicating the direction of the homogenous electron transfer reaction (Keq = 2.013). Similarly, to confirm the occurrence of the homogeneous electron transfer reaction between O2 and another quinone based molecule, cyclic voltammetry and bulk electrolysis experiments were carried out on 9,10-anthraquinone (AQ), and its equilibrium constant value was also obtained (Keq = 4.392).

Solvent and substituent effect on electrochemistry of ferrocenylcarboxylic acids

The redox properties of six ferrocenyl carboxylic acids (1–6) in dichloromethane and acetonitrile are compared. The formal reduction potential of Fe of the ferrocenyl group in these carboxylic acids occur ca. 0.1 V more positive in DCM than in CH3CN. The carboxylic group is directly connected to ferrocenyl, or by an ethene group, or by an alkyl chain of varying length. The length of the alkyl chain separating the two groups affected the formal reduction potential of Fe of the ferrocenyl group. The formal reduction potential was also affected by the electron-withdrawing carbonyl group. The extent of the effect depended on whether the carbonyl group was directly bound to a ferrocenyl moiety or, isolated by an sp3 hybridized carbon atom backbone (-CH2-CH2-) or a non-isolated sp2 hybridized carbon atom backbone (-CH=CH-). The results obtained were further validated by density functional theory (DFT) calculations on ferrocenyl carboxylic acids (1–6) as well as selected substituted ferrocenyl compounds from literature. A linear relationship between the formal reduction potential of substituted ferrocenes and DFT calculated HOMO energies were obtained.

Electro-kinetics of conversion of NO3− into NO2−and sensing of nitrate ions via reduction reactions at copper immobilized platinum surface in the neutral medium

The electrocatalytic reduction of NO3− in neutral medium was investigated at Cuelectro-deposited Pt electrodes. Inherently, the fabricated Pt–Cu electrode surface contains Cu (I) and Cu (II) oxides. The presence of these oxides decreases the efficiency of the electrode pertaining to nitrate reduction reactions (NRR). Since Cu (II) reduction wave and nitrate reduction wave appear closely, this makes complicated for proper kinetic analysis using a Pt–Cu electrode. Thus, oxide deficient electrode was fabricated in–situ by applying a deposition potential at – 0.45 V for 2 min prior to voltammetric scanning for NRR. The voltammetric investigations showed that the oxide deficit (OD) Pt– Cu electrode has an enhanced catalytic effect (i.e. positive shift of the peak potential and an increased reduction current) on NRR than an oxide rich (OR) Pt–Cu electrode. A nitrate ion (NO3−) is converted into a nitrite ion (NO2−) following a step-wise mechanism, where formal reduction potential and the standard rate constant was evaluated as −0.46 V (vs. Ag/AgCl (sat.KCl) ref. electrode) and 2.48 × 10−4 cm s−1, respectively. In diagnostic exploration, Differential pulse voltammograms (DPV) were recorded over a large concentration range of NO3− between 0.12 and 4.75 mM at room temperature, which exhibited linear relationship with two linear dynamic range (LDR) having a break point at 0.99 mM. This electrode displayed an excellent sensitivity (2.3782 μAμM−1cm−2), ultra-low detection limit (LOD: 0.159 μM; S/N = 3), long term stability, very good repeatability and reproducibility.

Proton-coupled electron transfer from an interfacial phenol monolayer

A tert-butyl protected phenol is covalently link to a mixed self-assembled monolayer on a gold or platinum electrode. The phenol reduction potential shows the expected pH-dependence of a one-electron, one-proton couple with a decrease in formal reduction potential of 59 ± 5 mV per pH. A titration of the phenol is observed with a pKa of 13.2 and the reduction potential for the phenolate is 0.11 V . NHE. The kinetic behavior of the proton-coupled oxidation deviates substantially from the commonly used models for a step-wise reaction that assume the proton transfer reactions are in equilibrium throughout the reaction. A novel model for step-wise proton-coupled reactions is presented that fully accounts for the pH dependent kinetics and allows the formal rate constants and the transfer coefficients to be determined.

Synthesis, Spectroscopy and Electrochemistry in Relation to DFT Computed Energies of Ferrocene- and Ruthenocene-Containing -Diketonato Iridium(III) Heteroleptic Complexes. Structure of [(2-Pyridylphenyl)2Ir(RcCOCHCOCH3

A series of new ferrocene- and ruthenocene-containing iridium(III) heteroleptic complexes of the type [(ppy)2Ir(RCOCHCOR′)], with ppy = 2-pyridylphenyl, R = Fc = FeII(η5-C5H4)(η5-C5H5) and R′ = CH3 (1) or Fc (2), as well as R = Rc = RuII(η5-C5H4)(η5-C5H5) and R′ = CH3 (3), Rc (4) or Fc (5) was synthesized via the reaction of appropriate metallocene-containing β-diketonato ligands with [(ppy)2(μ-Cl)Ir]2. The single crystal structure of 3 (monoclinic, P21/n, Z = 4) is described. Complexes 1–5 absorb light strongly in the region 280−480 nm the metallocenyl β-diketonato substituents quench phosphorescence in 1–5. Cyclic and square wave voltammetric studies in CH2Cl2/[N(nBu)4][B(C6F5)4] allowed observation of a reversible IrIII/IV redox couple as well as well-resolved ferrocenyl (Fc) and ruthenocenyl (Rc) one-electron transfer steps in 1−5. The sequence of redox events is in the order Fc oxidation, then IrIII oxidation and finally ruthenocene oxidation, all in one-electron transfer steps. Generation of IrIV quenched phosphorescence in 6, [(ppy)2Ir(H3CCOCHCOCH3)]. This study made it possible to predict the IrIII/IV formal reduction potential from Gordy scale group electronegativities, χR and/or ΣχR′ of β-diketonato pendent side groups as well as from DFT-calculated energies of the highest occupied molecular orbital of the species involved in the IrIII/IV oxidation at a 98% accuracy level.