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Probing quantum and dynamic effects in concerted proton-electron transfer reactions of phenol-base compounds.

ABSTRACT: The oxidation of three phenols, which contain an intramolecular hydrogen bond to a pendent pyridine or amine group, has been shown, in a previous experimental study, to undergo concerted proton-electron transfer (CPET). In this reaction, the electron is transferred to an outer-sphere oxidant, and the proton is transferred from the oxygen to nitrogen atom. In the present study, this reaction is studied computationally using a version of Hammes-Schiffer's multistate continuum theory where CPET is formulated as a transmission frequency between neutral and cation vibrational-electronic states. The neutral and cation proton vibrational wave functions are computed from one-dimensional potential energy surfaces (PESs) for the transferring proton in a fixed heavy atom framework. The overlap integrals for these neutral/cation wave functions, considering several initial (i.e., neutral) and final (i.e., cation) vibrational states, are used to evaluate the relative rates of oxidation. The analysis is extended to heavy atom configurations with various proton donor-acceptor (i.e., O-N) distances to assess the importance of heavy atom "gating". Such changes in d(ON) dramatically affect the nature of the proton PESs and wave functions. Surprisingly, the most reactive configurations have similar donor-acceptor distances despite the large (~0.2 Å) differences in the optimized structures. These theoretical results qualitatively reproduce the experimental faster reactivity of the reaction of the pyridyl derivative 1 versus the CH(2)-pyridyl 2, but the computed factor of 5 is smaller than the experimental 10(2). The amine derivative is calculated to react similarly to 1, which does not agree with the experiments, likely due to some of the simplifying assumptions made in applying the theory. The computed kinetic isotope effects (KIEs) and their temperature dependence are in agreement with experimental results.

SUBMITTER: Markle TF

PROVIDER: S-EPMC3974916 | biostudies-literature | 2012 Jan

REPOSITORIES: biostudies-literature

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Probing quantum and dynamic effects in concerted proton-electron transfer reactions of phenol-base compounds.

Markle Todd F TF Tenderholt Adam L AL Mayer James M JM

The journal of physical chemistry. B 20111223 1

The oxidation of three phenols, which contain an intramolecular hydrogen bond to a pendent pyridine or amine group, has been shown, in a previous experimental study, to undergo concerted proton-electron transfer (CPET). In this reaction, the electron is transferred to an outer-sphere oxidant, and the proton is transferred from the oxygen to nitrogen atom. In the present study, this reaction is studied computationally using a version of Hammes-Schiffer's multistate continuum theory where CPET is ...[more]

PMID: 22148459

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Project description:The coupling between electrons and protons and the long-range transport of protons play important roles throughout biology. Biomimetic systems derived from benzimidazole-phenol (BIP) constructs have been designed to undergo proton-coupled electron transfer (PCET) upon electrochemical or photochemical oxidation. Moreover, these systems can transport protons along hydrogen-bonded networks or proton wires through multiproton PCET. Herein, the nonequilibrium dynamics of both single and double proton transfer in BIP molecules initiated by oxidation are investigated with first-principles molecular dynamics simulations. Although these processes are concerted in that no thermodynamically stable intermediate is observed, the simulations predict that they are predominantly asynchronous on the ultrafast time scale. For both systems, the first proton transfer typically occurs ∼100 fs after electron transfer. For the double proton transfer system, typically the second proton transfer occurs hundreds of femtoseconds after the initial proton transfer. A machine learning algorithm was used to identify the key molecular vibrational modes essential for proton transfer: a slow, in-plane bending mode that dominates the overall inner-sphere reorganization, the proton donor-acceptor motion that leads to vibrational coherence, and the faster donor-hydrogen stretching mode. The asynchronous double proton transfer mechanism can be understood in terms of a significant mode corresponding to the two anticorrelated proton donor-acceptor motions, typically decreasing only one donor-acceptor distance at a time. Although these PCET processes appear concerted on the time scale of typical electrochemical experiments, attaching these BIP constructs to photosensitizers may enable the detection of the asynchronicity of the electron and multiple proton transfers with ultrafast two-dimensional spectroscopy. Understanding the fundamental PCET mechanisms at this level will guide the design of PCET systems for catalysis and energy conversion processes.

Project description:Photo-oxidations of hydrogen-bonded phenols using excited-state polyarenes are described to derive fundamental understanding of multiple-site concerted proton-electron transfer reactions (MS-CPET). Experiments have examined phenol bases having -CPh(2)NH(2), -Py, and -CH(2)Py groups ortho to the phenol hydroxyl group and tert-butyl groups in the 4,6-positions for stability (HOAr-NH(2), HOAr-Py, and HOAr-CH(2)Py, respectively; Py = pyridyl; Ph = phenyl). The photo-oxidations proceed by intramolecular proton transfer from the phenol to the pendent base concerted with electron transfer to the excited polyarene. For comparison, 2,4,6-(t)Bu(3)C(6)H(2)OH, a phenol without a pendent base and tert-butyl groups in the 2,4,6-positions, has also been examined. Many of these bimolecular reactions are fast, with rate constants near the diffusion limit. Combining the photochemical k(CPET) values with those from prior thermal stopped-flow kinetic studies gives data sets for the oxidations of HOAr-NH(2) and HOAr-CH(2)Py that span over 10(7) in k(CPET) and nearly 0.9 eV in driving force (ΔG(o)'). Plots of log(k(CPET)) vs ΔG(o)', including both excited-state anthracenes and ground state aminium radical cations, define a single Marcus parabola in each case. These two data sets are thus well described by semiclassical Marcus theory, providing a strong validation of the use of this theory for MS-CPET. The parabolas give λ(CPET) ≅ 1.15-1.2 eV and H(ab) ≅ 20-30 cm(-1). These experiments represent the most direct measurements of H(ab) for MS-CPET reactions to date. Although rate constants are available only up to the diffusion limit, the parabolas clearly peak well below the adiabatic limit of ca. 6 × 10(12) s(-1). Thus, this is a very clear demonstration that the reactions are nonadiabatic. The nonadiabatic character slows the reactions by a factor of ~45. Results for the oxidation of HOAr-Py, in which the phenol and base are conjugated, and for oxidation of 2,4,6-(t)Bu(3)C(6)H(2)OH, which lacks a base, show that both have substantially lower λ and larger pre-exponential terms. The implications of these results for MS-CPET reactions are discussed.

Dataset Information

Probing quantum and dynamic effects in concerted proton-electron transfer reactions of phenol-base compounds.

Publications

Probing quantum and dynamic effects in concerted proton-electron transfer reactions of phenol-base compounds.

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