Proton-coupled electron transfer.
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ABSTRACT:
SUBMITTER: Huynh MH
PROVIDER: S-EPMC3449329 | biostudies-literature | 2007 Nov
REPOSITORIES: biostudies-literature
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Project description:Multiple-site concerted proton-electron transfer (MS-CPET) reactions were studied in a three-component system. 1-Hydroxy-2,2,6,6-tetramethylpiperidine (TEMPOH) was oxidized to the stable radical TEMPO by electron transfer to ferrocenium oxidants coupled to proton transfer to various pyridine bases. These MS-CPET reactions contrast with the usual reactivity of TEMPOH by hydrogen atom transfer (HAT) to a single e-/H+ acceptor. The three-component reactions proceed by pre-equilibrium formation of a hydrogen-bonded adduct between TEMPOH and the pyridine base, and the adduct is then oxidized by the ferrocenium in a bimolecular MS-CPET step. The second-order rate constants, measured using stopped-flow kinetic techniques, spanned 4 orders of magnitude. An advantage of this system is that the MS-CPET driving force could be independently varied by changing either the pKa of the base or the reduction potential (E°) of the oxidant. Changes in ΔG°MS-CPET from either source had the same effect on the MS-CPET rate constants, and a combined Brønsted plot of ln(kMS-CPET) vs ln(Keq) was linear with a slope of 0.46. These results imply a synchronous concerted mechanism, in which the proton and electron transfer components of the CPET process make equal contributions to the rate constants. The only outliers to the Brønsted correlation are the reactions with sterically hindered pyridines, which apparently hinder the close approach of proton donor and acceptor that facilitates MS-CPET. These three-component reactions are compared with a related HAT reaction of TEMPOH, with the 2,4,6-tri-tert-butylphenoxyl radical. The MS-CPET and HAT oxidations of TEMPOH at the same driving force occurred with similar rate constants. While this is an imperfect comparison, the data suggest that the separation of the proton and electron to different reagents does not significantly inhibit the proton-coupled electron transfer process.
| S-EPMC5812448 | biostudies-literature
Project description:Proton-coupled electron transfer (PCET) reactions are fundamental to energy transformation reactions in natural and artificial systems and are increasingly recognized in areas such as catalysis and synthetic chemistry. The interdependence of proton and electron transfer brings a mechanistic richness of reactivity, including various sequential and concerted mechanisms. Delineating between different PCET mechanisms and understanding why a particular mechanism dominates are crucial for the design and optimization of reactions that use PCET. This Perspective provides practical guidelines for how to discern between sequential and concerted mechanisms based on interpretations of thermodynamic data with temperature-, pressure-, and isotope-dependent kinetics. We present new PCET-zone diagrams that show how a mechanism can switch or even be eliminated by varying the thermodynamic (ΔGPT° and ΔGET°) and coupling strengths for a PCET system. We discuss the appropriateness of asynchronous concerted PCET to rationalize observations in organic reactions, and the distinction between hydrogen atom transfer and other concerted PCET reactions. Contemporary issues and future prospects in PCET research are discussed.
| S-EPMC7880575 | biostudies-literature
Project description: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-o-carboranes 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 o-carborane (PhCbPhN) can be reduced and protonated to generate an N-H bond with a weak effective bond dissociation free energy (BDFEeff) 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.
| S-EPMC11544690 | biostudies-literature
Project description: Not available
| S-EPMC4317057 | biostudies-literature
Project description:Photoinduced proton-coupled electron transfer and long-range two-proton transport via a Grotthuss-type mechanism are investigated in a biomimetic construct. The ultrafast, nonequilibrium dynamics are assessed via two-dimensional electronic vibrational spectroscopy, in concert with electrochemical and computational techniques. A low-frequency mode is identified experimentally and found to promote double proton and electron transfer, supported by recent theoretical simulations of a similar but abbreviated (non-photoactive) system. Excitation frequency peak evolution and center line slope dynamics show direct evidence of strongly coupled nuclear and electronic degrees of freedom, from which we can conclude that the double proton and electron transfer processes are concerted (up to an uncertainty of 24 fs). The nonequilibrium pathway from the photoexcited Franck-Condon region to the E2PT state is characterized by an ∼110 fs time scale. This study and the tools presented herein constitute a new window into hot charge transfer processes involving an electron and multiple protons.
| S-EPMC9150097 | biostudies-literature
Project description:Designing molecular platforms for controlling proton and electron movement in artificial photosynthetic systems is crucial to efficient catalysis and solar energy conversion. The transfer of both protons and electrons during a reaction is known as proton-coupled electron transfer (PCET) and is used by nature in myriad ways to provide low overpotential pathways for redox reactions and redox leveling, as well as to generate bioenergetic proton currents. Herein, we describe theoretical and electrochemical studies of a series of bioinspired benzimidazole-phenol (BIP) derivatives and a series of dibenzimidazole-phenol (BI2P) analogs with each series bearing the same set of terminal proton-accepting (TPA) groups. The set of TPAs spans more than 6 pK a units. These compounds have been designed to explore the role of the bridging benzimidazole(s) in a one-electron oxidation process coupled to intramolecular proton translocation across either two (the BIP series) or three (the BI2P series) acid/base sites. These molecular constructs feature an electrochemically active phenol connected to the TPA group through a benzimidazole-based bridge, which together with the phenol and TPA group form a covalent framework supporting a Grotthuss-type hydrogen-bonded network. Infrared spectroelectrochemistry demonstrates that upon oxidation of the phenol, protons translocate across this well-defined hydrogen-bonded network to a TPA group. The experimental data show the benzimidazole bridges are non-innocent participants in the PCET process in that the addition of each benzimidazole unit lowers the redox potential of the phenoxyl radical/phenol couple by 60 mV, regardless of the nature of the TPA group. Using a series of hypothetical thermodynamic steps, density functional theory calculations correctly predicted the dependence of the redox potential of the phenoxyl radical/phenol couple on the nature of the final protonated species and provided insight into the thermodynamic role of dibenzimidazole units in the PCET process. This information is crucial for developing molecular "dry proton wires" with these moieties, which can transfer protons via a Grotthuss-type mechanism over long distances without the intervention of water molecules.
| S-EPMC8152432 | biostudies-literature
Project description:Here we report a ternary catalyst system for the intramolecular hydroamidation of unactivated olefins using simple N-aryl amide derivatives. Amide activation in these reactions occurs via concerted proton-coupled electron transfer (PCET) mediated by an excited state iridium complex and weak phosphate base to furnish a reactive amidyl radical that readily adds to pendant alkenes. A series of H-atom, electron, and proton transfer events with a thiophenol cocatalyst furnish the product and regenerate the active forms of the photocatalyst and base. Mechanistic studies indicate that the amide substrate can be selectively homolyzed via PCET in the presence of the thiophenol, despite a large difference in bond dissociation free energies between these functional groups.
| S-EPMC4629195 | biostudies-literature
Project description:Figuring out the specific pathway of semiconductor-mediated proton-coupled electron transfer (PCET) driven by light is essential to solar energy conversion systems. In this work, we reveal that the amount of adsorbed water molecules determines the photo-induced PCET pathway on the TiO2 surface through systematic kinetic solvent isotope effect (KSIE) experiments. At low water content (<1.7 wt%), the photo-induced single-proton/single-electron transfer on TiO2 nanoparticles follows a stepwise PT/ET pathway with the formation of high-energy H+/D+-O[double bond, length as m-dash]C or H+/D+-O-C intermediates, resulting in an inverse KSIE (H/D) ∼0.5 with t Bu3ArO· and KSIE (H/D) ∼1 with TEMPO in methanol-d 0/d 4 systems. However, at high water content (>2 wt%), the PCET reaction follows a concerted pathway with a lower energy barrier, leading to normal KSIEs (H/D) ≥ 2 with both reagents. In situ ATR-FTIR observation and DFT calculations suggest that water molecules' existence significantly lowers the proton/electron transfer energy barrier, which coincides with our experimental observations.
| S-EPMC10155922 | biostudies-literature
Project description:The alternative oxidase (AOX) is a membrane-bound di-iron enzyme that catalyzes O2-driven quinol oxidation in the respiratory chains of plants, fungi, and several pathogenic protists of biomedical and industrial interest. Yet, despite significant biochemical and structural efforts over the last decades, the catalytic principles of AOX remain poorly understood. We develop here multi-scale quantum and classical molecular simulations in combination with biochemical experiments to address the proton-coupled electron transfer (PCET) reactions responsible for catalysis in AOX from Trypanosoma brucei, the causative agent of sleeping sickness. We show that AOX activates and splits dioxygen via a water-mediated PCET reaction, resulting in a high-valent ferryl/ferric species and tyrosyl radical (Tyr220˙) that drives the oxidation of the quinol via electric field effects. We identify conserved carboxylates (Glu215, Asp100) within a buried cluster of ion-pairs that act as a transient proton-loading site in the quinol oxidation process, and validate their function experimentally with point mutations that result in drastic activity reduction and pK a-shifts. Our findings provide a key mechanistic understanding of the catalytic machinery of AOX, as well as a molecular basis for rational drug design against energy transduction chains of parasites. On a general level, our findings illustrate how redox-triggered conformational changes in ion-paired networks control the catalysis via electric field effects.
| S-EPMC11492382 | biostudies-literature
Project description:The use of light to drive proton-coupled electron transfer (PCET) reactions has received growing interest, with recent focus on the direct use of excited states in PCET reactions (ES-PCET). Electrostatic ion pairs provide a scaffold to reduce reaction orders and have facilitated many discoveries in electron-transfer chemistry. Their use, however, has not translated to PCET. Herein, we show that ion pairs, formed solely through electrostatic interactions, provide a general, facile means to study an ES-PCET mechanism. These ion pairs formed readily between salicylate anions and tetracationic ruthenium complexes in acetonitrile solution. Upon light excitation, quenching of the ruthenium excited state occurred through ES-PCET oxidation of salicylate within the ion pair. Transient absorption spectroscopy identified the reduced ruthenium complex and oxidized salicylate radical as the primary photoproducts of this reaction. The reduced reaction order due to ion pairing allowed the first-order PCET rate constants to be directly measured through nanosecond photoluminescence spectroscopy. These PCET rate constants saturated at larger driving forces consistent with approaching the Marcus barrierless region. Surprisingly, a proton-transfer tautomer of salicylate, with the proton localized on the carboxylate functional group, was present in acetonitrile. A pre-equilibrium model based on this tautomerization provided non-adiabatic electron-transfer rate constants that were well described by Marcus theory. Electrostatic ion pairs were critical to our ability to investigate this PCET mechanism without the need to covalently link the donor and acceptor or introduce specific hydrogen bonding sites that could compete in alternate PCET pathways.
| S-EPMC8152629 | biostudies-literature