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Observation of super-Nernstian proton-coupled electron transfer behavior with two protons per electron transferred in an electrochemically n-doped redox conjugated polymer.
Here, we present an update and revision to our 2010 review on the topic of proton- coupled electron transfer (PCET) reagent thermochemistry. Over the past decade, the data and thermochemical formalisms presented in that review have been of value to multiple fields. Concurrently, there have been advances in the thermochemical cycles and experimental methods used to measure these values. This Review (i) summarizes those advancements, (ii) corrects systematic errors in our prior review that shifted many of the absolute values in the tabulated data, (iii) provides updated tables of thermochemical values, and (iv) discusses new conclusions and opportunities from the assembled data and associated techniques. We advocate for updated thermochemical cycles that provide greater clarity and reduce experimental barriers to the calculation and measurement of Gibbs free energies for the conversion of X to XHn in PCET reactions. In particular, we demonstrate the utility and generality of reporting potentials of hydrogenation, E°(V vs H 2 ), in almost any solvent and how these values are connected to more widely reported bond dissociation free energies (BDFEs). The tabulated data demonstrate that E°(V vs H 2 ) and BDFEs are generally insensitive to the nature of the solvent and, in some cases, even to the phase (gas versus solution). This Review also presents introductions to several emerging fields in PCET thermochemistry to give readers windows into the diversity of research being performed. Some of the next frontiers in this rapidly growing field are coordination-induced bond weakening, PCET in novel solvent environments, and reactions at material interfaces.
Here, the oxidation of metal-aquo and -hydroxo complexes to generate the high-valent metal-oxo species used in oxidative catalysis is often kinetically slow due to sluggish proton transfer between ligated −H 2 O/–OH in the proton-coupled electron transfer (PCET) chemistry. In this research, a ruthenium water oxidation catalyst anchored to a conductive tin-doped indium oxide (ITO) thin film, abbreviated ITO|Ru II –OH 2 , was characterized by spectroscopic and electrochemical methods in acetate or phosphate buffers. The deprotonated intermediate, Ru II –OH, was observed spectroscopically in the PCET half-reaction ITO(e – )|Ru III –OH + H + → ITO|Ru II –OH 2 indicating an underlying stepwise ET-PT mechanism. In contrast, at elevated buffer concentrations, this intermediate was absent, and a 2–4 order of magnitude increase in the proton transfer rate constant was observed. Kinetic data for this PCET reaction measured as a function of the driving force provided the reorganization energy λ = 1.05 eV and was assigned to a concerted electron–proton transfer (EPT) mechanism. In addition, the standard heterogeneous rate constants for two PCET equilibria, Ru III –OH + H + + e – ⇌ Ru II –OH 2 and Ru IV = O + H + + e – ⇌ Ru III –OH were enhanced by these same buffers. Collectively, the data show that the added buffers can enhance the kinetics and thermodynamics for PCET reactions relevant to oxidative catalysis.
In this work, proton-coupled electron transfer (PCET) was studied for the ground and excited electronic states of a [Ru(terpy)(bpm)(OH 2 )(PF 6 ) 2 ] complex, Ru-bpm. Cyclic voltammetry measurements show that the Ru(II)-aqua moiety undergoes PCET to form a Ru(IV)-oxo moiety in the anodic region, while the bpm ligand undergoes PCET to form bpmH 2 in the cathodic region. The photophysical behavior of Ru-bpm was studied using steady-state and femtosecond transient UV–vis absorption spectroscopy, coupled with density functional theory (DFT) calculations. The lowest-lying excited state of Ru-bpm is described as a (Ru → bpm) metal-to-ligand charge-transfer (MLCT) state, while the metal-centered (MC) excited state was found computationally to be close in energy to the lowest-energy bright MLCT state (MC state was 0.16 eV above the MLCT state). The excited-state kinetics of Ru-bpm were found via transient absorption spectroscopy to be short-lived and were fit well to a biexponential function with lifetimes $τ_1$ = 4 ps and $τ_2$ = 65 ps in aqueous solution. Kinetic isotope effects of 1.75 ($τ_1$) and 1.61 ($τ_2$) were observed for both decay components, indicating that the solvent plays an important role in the excited-state dynamics of Ru-bpm. Based on the pH-dependent studies and the results from prior studies of similar Ru-complexes, we hypothesize that the 3 MLCT state forms an excited-state hydrogen-bond adduct with the solvent molecules and that this process occurs with a 4 ps lifetime. The formation of such a hydrogen-bond complex is consistent with the electronic density accumulation at the peripheral N atoms of the bpm moiety in the 3 MLCT state. The hydrogen-bonded state 3 MLCT decays to the ground state with a 65 ps lifetime. Such a short lifetime is likely associated with the efficient vibrational energy transfer from the 3 MLCT state to the solvent.
The rate of charge transfer within a discrete donor–acceptor (D/A) pair is well-described by semi-classical electron transfer theory, but the effects of multiple equivalent redox sites remain less understood. We report a series of ground-state intramolecular proton-coupled electron transfer (PCET) complexes designed to isolate the effects of donor number, N, while holding geometry, coupling, and driving forces constant. The [Ru(L) 3−N (OH) N ] 2+ complexes incorporate one, two, or three identical phenolic electron donors linked to Ru through rigid phenanthroline bridges (OH = 2,4-di-tert-butyl-6-(1-methyl-1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenol). Upon flash photolysis and oxidative quenching with methyl viologen (MV 2+ ), the transient Ru(III) oxidizes an appended phenol by PCET with the hydrogen-bonded imidazole nitrogen atom functioning as the base. The rate increased by 3.4-fold and 5.7-fold (1.7-fold and 1.9-fold after statistical correction) for two- and three-donor complexes compared to the single-donor system. The supra-statistical acceleration is attributed to a reduced effective outer sphere reorganization energy (λ m ) modeled by a partially shared solvent reaction coordinate, in which a subset of solvent dipoles is already oriented to stabilize charge from any donor. The final phenoxyl radical state is localized due to the transfer of a proton, and the recombination reaction with the viologen radical is not accelerated. These results demonstrate the effects of solvent dynamics on intramolecular PCET rates, offering a new strategy for the design of synthetic charge transfer systems.
An externally exposed V dopant imposes H-atom uptake at the polyoxotungstate surface and dictates the proton–coupled electron transfer mechanism.
The oxidation of phenolic compounds is one of the most important reactions prevalent in various biological processes, often explicitly coupled with proton transfers (PTs). Quantitative descriptions and molecular-level understanding of these proton-coupled electron transfer (PCET) reactions have been challenging. This work reports a direct observation of PCET in photodetachment (PD) photoelectron spectroscopy (PES) of hydrogen-bonded phenolic (ArOH) nitrate (NO 3 - ) complexes, in which a much slower rising edge provides a spectroscopic signature to evidence PCET. Electronic structure calculations unveil the PCET processes to be isomer-specific, occurred only in those with their HOMOs localized on ArOH, leading to charge-separated transient states ArOH •+ ·NO 3 - triggered by ionizing phenols while simultaneously promoting PT from ArOH •+ to NO 3 - . Importantly, this study showcases that gas-phase PD-PES is a generic means enabling to identify PCET reactions with explicit structural and binding information.
Redox reactions of aqueous colloidal TiO 2 4 nm nanoparticles (NPs) have been examined, including both citratecapped and uncapped NPs (c-TiO 2 and uc-TiO 2 ). Photoreduction gave stable blue colloidal c-TiO 2 R NPs with 10–60 electrons per particle. Equilibration of these reduced NPs with soluble redox reagents such as methylviologen (MV 2+ ) provided measurements of the colloid reduction potential as a function of pH. The potentials of c-TiO 2 from pH 2–9 varied linearly with pH, with a slope of –60 ± 5 mV/pH. Estimates of the potential at pH 12 were consistent with extrapolating that line to high pH. The reduction potentials did not correlate with the zeta potentials (ζ) or the surface charge of the NPs across this pH range. Similar reduction potentials were observed for c- and uc-TiO 2 at low pH even though they have quite different ζ potentials. These results show that the common surface-charging explanation of the pH dependence is not tenable in these systems. Oxidation of reduced c-TiO 2 R with the electron-transfer oxidant potassium triiodide (KI 3 ) occurred with a significant drop in pH, showing that protons were released when the electrons were removed from the NPs. Smaller pH drops were observed for the proton-coupled electron transfer (PCET) reagents O 2 (air) and 4-MeO-TEMPO (4-methoxy-2,2,6,6-tetramethylpiperine-1-oxy radical). The difference in the number of protons released with KI 3 vs O 2 and 4-MeO-TEMPO was roughly one proton per electron removed. Thus, the thermodynamically preferred reactivity of these colloidal TiO 2 NPs is PCET over the pH 2–13 range studied. The measured redox potentials refer to the chemical process TiO 2 + H + + e – → TiO 2 ·e – ,H + ; and therefore they do not correspond with an electronic energy such as a conduction band edge or flat band potential. The 1e – /1H + stoichiometry means that the TiO 2 reduction potentials correspond to a TiO 2 –H bond dissociation free energy (BDFE), determined to be 49 ± 2 kcal mol –1 . The PCET description is consistent with the pH dependence of E(TiO 2 /TiO 2 ·e – ,H + ), the release of protons upon oxidation, the lack of correlation with ζ potentials, the similarity of capped and uncapped NPs, and the small change in the potential and BDFE from the first to the last electron/proton pair (H atom) removed. Furthermore, this behavior is suggested to be the norm for redox-active oxide/water interfaces.
Electrochemical CO 2 separation has drawn attention as a promising strategy for using renewable energy to mitigate climate change. Redox-active compounds that undergo proton-coupled electron transfer (PCET) are an impetus for pH-swing-driven CO 2 capture at low energetic costs. However, multiple barriers hinder this technology from maturing, including sensitivity to oxygen and the slow kinetics of CO 2 capture. Here, we use vapor phase chemistry to construct a textile electrode comprising an immobilized PCET agent, poly(1-aminoanthraquinone) (PAAQ), and incorporate it into redox flow cells. This design contrasts with others that use dissolved PCET agents by confining proton-storage to the surface of an electrode kept separate from an aqueous, CO 2 -capturing phase. This system facilitates carbon capture from gaseous sources (a 1% CO 2 feed and air), as well as seawater, with the latter at an energetic cost of 202 kJ/mol CO2 , and we find that quinone moieties embedded within the electrode are more stable to oxygen than dissolved counterparts. Simulations using a 1D reaction-transport model show that moderate energetic costs should be possible for air capture of CO 2 with higher loadings of polymer-bound PCET moieties. The remarkable stability of this system sets the stage for producing textile-based electrodes that facilitate pH-swing-driven carbon capture in practical situations.
An earth-abundant Cu( i ) chromophore-anthraquinone dyad is reported to photochemically accumulate two electrons at the anthraquinone via proton-coupled electron transfer, generating the monoprotonated photoproduct.
Reagents capable of concerted proton–electron transfer (CPET) reactions can access reaction pathways with lower reaction barriers compared to stepwise pathways involving electron transfer (ET) and proton transfer (PT). To realize reductive multielectron/proton transformations involving CPET, one approach that has shown recent promise involves coupling a cobaltocene ET site with a protonated arylamine Brønsted acid PT site. This strategy colocalizes the electron/proton in a matter compatible with a CPET step and net reductive electrocatalysis. To probe the generality of such an approach a class of C,C'-diaryl-ocarboranes is herein explored as a conceptual substitute for the cobaltocene subunit, with an arylamine linkage still serving as a colocalized Brønsted base suitable for protonation. The featured ocarborane (PhCbPh N ) can be reduced and protonated to generate an N–H bond with a weak effective bond dissociation free energy (BDFE eff ) of 31 kcal/mol, estimated with measured thermodynamic data. This N–H bond is among the lowest measured element–H bonds for analyzed nonmetal compounds. Distinct solid-state crystal structures of the one- and two-electron reduced forms of diaryl-o-carboranes are disclosed to gain insight into their well-behaved redox characteristics. The singly reduced, protonated form of the diaryl-o-carborane can mediate multi-ET/PT reductions of azoarenes, diphenylfumarate, and nitrotoluene. In contrast to the aforementioned cobaltocene system, available mechanistic data disclosed herein support these reactions occurring by a rate-limiting ET step and not a CPET step. A relevant hydrogen evolution reaction (HER) reaction was also studied, with data pointing to a PT/ ET/PT mechanism, where the reduced carborane core is itself highly stable to protonation.
Human manganese superoxide dismutase (MnSOD) plays a crucial role in controlling levels of reactive oxygen species (ROS) by converting superoxide (O$^{•–}_{2}$) to molecular oxygen (O 2 ) and hydrogen peroxide (H 2 O 2 ) with proton-coupled electron transfers (PCETs). A key catalytic residue, Tyr34, determines the activity of human MnSOD and also becomes post-translationally inactivated by nitration in various diseases associated with mitochondrial dysfunction. Tyr34 has an unusual pK a due to its proximity to the Mn metal and undergoes cyclic deprotonation and protonation events to promote the electron transfers of MnSOD. Neutron diffraction, X-ray spectroscopy, and quantum chemistry calculations in oxidized, reduced and product inhibited enzymatic states shed light on the role of Tyr34 in MnSOD catalysis. The data identify the contributions of Tyr34 in MnSOD activity that support mitochondrial function and give a thorough characterization of how a single tyrosine modulates PCET catalysis. Product inhibition occurs by an associative displacement mechanism.
Concentrated hydrogen-bonded electrolytes (CoHBEs) are structured, electrochemically stable, less-volatile alternatives to aqueous and dilute nonaqueous electrolytes, however, with high viscosities that limit molecular diffusion. This work provides an understanding of the proton conduction mechanism in CoHBEs based on mixtures of acids and azoles and establishes a link between the structurally dictated transport properties and the proton-coupled electron transfer (PCET) reaction rates that can be leveraged for enhancing electrochemical reactions. Diffusion and relaxation NMR studies suggest a breaking of the viscosity–conductivity tradeoff, where at high azole concentrations (>45 mol%), Grotthuss transport is more likely with lowered proton transfer energy barriers between the azole and the acid according to the machine learning (ML) accelerated ab initio path integral MD (AI-PIMD) simulations. Proton conduction pathways are found to be switchable between the hydrogen bonding networks of the acid and the azole, with imidazole chain forming structures better facilitating Grotthuss hopping. Supported by small-angle neutron scattering studies, the chains are found to have six member molecules on average with maximum of 3 to 4 imidazole/imidazoliums at 50 to 60 mol%. Despite their high viscosities, the measured PCET rates for quinones and phenazines measured in the protic CoHBEs present relatively high electron transfer rate constants (k 0 ~ 10 −4 cm/s), validated by rotating disc electrode and scanning electrochemical microscopy measurements. The results demonstrate that strategic tuning of hydrogen-bond donor–acceptor interactions enables the decoupling of proton transport and viscosity, thereby impacting PCET reactions.
Enantioselective hydrogenation of C═C bonds is foundational to asymmetric synthesis, yet its adaptation to electrochemical methods has been limited by challenges in achieving chemoselectivity versus the hydrogen evolution reaction (HER). In this article, we present a modular electrochemical strategy that merges chiral nickel catalysis with a cobaltocene-derived proton-coupled electron transfer (PCET) mediator to enable the asymmetric hydrogenation of α,β-unsaturated carbonyl compounds. Under optimized conditions, a range of substrates featuring diverse amide functionalities and substitution patterns are hydrogenated in high yields (up to 95%) and enantioselectivities (up to 98% ee). The results described highlight the potential benefits of mediator-assisted, fixed-potential electrocatalysis in selective, stereocontrolled hydrogenation under mild conditions.
Significance The chemical reduction of unsaturated bonds occurs by hydrogenation with H 2 as the reductant. Conversely, in biology, the unavailability of H 2 engenders the typical reduction of unsaturated bonds with electrons and protons from different cofactors, requiring olefin hydrogenation to occur by proton-coupled electron transfer (PCET). Moreover, the redox noninnocence of tetrapyrrole macrocycles furnishes unusual PCET intermediates, including the phlorin, which is an intermediate in tetrapyrrole ring reductions. Whereas the phlorin of a porphyrin is well established, the phlorin of a chlorin is enigmatic. By controlling the PCET reactivity of a chlorin, including the use of a hangman functionality to manage the proton transfer, the formation of a chlorinphlorin by PCET is realized, and the mechanism for its formation is defined.
Brønsted-Evans-Polanyi (BEP) relationships, which relate elementary reaction barriers to reaction thermodynamics, have long been discussed in electrochemical science, but demonstration of their existence in heterogeneous electrocatalysis, across many different catalyst surfaces and voltages, is lacking. In this contribution, the BEP model is demonstrated to describe both multiple catalyst surfaces and variable voltages in electrochemical environments. For proton-coupled electron transfer (PCET) to surface nitrogen (N*) and nitric oxide (NO*), reaction energies and activation barriers are calculated using Density Functional Theory (DFT) on a parallel plate capacitor model at three different potentials and for nine different transition metal surfaces. Linear BEP relations that describe all potentials and catalyst surfaces are obtained for these elementary reactions, and the slopes of the correlations are shown to be directly related to the fractional coordinate of the transition states (FCTS) of the reactions. The results, which are explained in terms of Marcus Theory, prove a direct equivalence between unified BEP coefficients, describing both variable catalyst surfaces and voltages, and electrochemical symmetry factors and provide a straightforward means of estimating this quantify for PCET reactions on transition metal surfaces. The resulting relationships, in turn, could lead to predictions of electrocatalytic reactivity trends of enhanced accuracy and efficiency.
Acid-functionalization of carbon support allows enhancing the electrocatalytic activity of Pd to hydrogenate benzaldehyde to benzyl alcohol in proportion to the concentration of Brønsted acid sites. The hydrogenation rate is not enhanced when H2 is used. The rate enhancement is attributed to differences in the hydrogenation mechanism between the electrochemical and the H2 induced hydrogenations, in particular to the participation of hydronium ions formed at Brønsted acid sites at the perimeter of metal particles in proton coupled electron transfer.
The pyridine(diimine) molybdenum bis(imido) complex, ( iPr PDI)Mo(=NTol) 2 (Tol = 4-methylphenyl) was synthesized by addition of two equivalents of 4-methylphenylazide to a corresponding molybdenum benzene derivative, ( iPr PDI)Mo(η 6 -C 6 H 6 ) ( iPr PDI = 2,6-(2,6-iPr 2 C 6 H 3 N=CMe) 2 C 5 H 3 N). Protonation of ( iPr PDI)Mo(=NTol) 2 with 2,6-lutinidum triflate yielded a cationic molybdenum amido complex, [( iPr PDI)Mo(NHTol)(=NTol)][OTf], which was further transformed into the neutral molybdenum amido complex, ( iPr PDI)Mo(NHTol)(=NTol) by reduction with zinc powder. A series of spectroscopic, synthetic and pK a determination studies along with electrochemical measurements by the protonation-reduction pathway were used to establish an N–H bond dissociation free energy (BDFE) between 65-69 kcal/mol for the molybdenum imido-amido compound, ( iPr PDI)Mo(NHTol)(=NTol). Full molecule DFT studies provided a computed value of 61 kcal/mol. By contrast, reduction of ( iPr PDI)Mo(=NTol) 2 with KC 8 afforded the corresponding anionic molybdenum complex, K[( iPr PDI)Mo(=NTol) 2 ] that has a potassium cation intercalated with the pyridine and the tolyl groups. Protonation of K[( iPr PDI)Mo(=NTol) 2 ] with the weak amidinium acids [TBD(H)][BArF 24 ] (TBD = triazabicyclodecene, BArF 24 = B[3,5-(CF 3 ) 2 C 6 H 3 ] 4 ) also produced the neutral molybdenum amido complex, ( iPr PDI)Mo(NHTol)(=NTol). Measurement of the pKa and oxidation potential of K[( iPr PDI)Mo(=NTol) 2 ] provided a range of 69-73 kcal/mol for the N–H BDFE of ( iPr PDI)Mo(NHTol)(=NTol), in good agreement with the protonation-reduction route and completing the square scheme. The similar pK a and redox potentials obtained from each pathway demonstrate that both sequences are energetically feasible for PCET events. This study on the determination of N–H BDFE of the molybdenum amido complex renders fundamental insight into the N 2 reduction cycle by proton-coupled electron transfer.