Dataset Information

C-H oxidation in fluorenyl benzoates does not proceed through a stepwise pathway: revisiting asynchronous proton-coupled electron transfer.

ABSTRACT: 2-Fluorenyl benzoates were recently shown to undergo C-H bond oxidation through intramolecular proton transfer coupled with electron transfer to an external oxidant. Kinetic analysis revealed unusual rate-driving force relationships. Our analysis indicated a mechanism of multi-site concerted proton-electron transfer (MS-CPET) for all of these reactions. More recently, an alternative interpretation of the kinetic data was proposed to explain the unusual rate-driving force relationships, invoking a crossover from CPET to a stepwise mechanism with an initial intramolecular proton transfer (PT) (Costentin, Savéant, Chem. Sci., 2020, 11, 1006). Here, we show that this proposed alternative pathway is untenable based on prior and new experimental assessments of the intramolecular PT equilibrium constant and rates. Measurement of the fluorenyl 9-C-H pK _a, H/D exchange experiments, and kinetic modelling with COPASI eliminate the possibility of a stepwise mechanism for C-H oxidation in the fluorenyl benzoate series. Implications for asynchronous (imbalanced) MS-CPET mechanisms are discussed with respect to classical Marcus theory and the quantum-mechanical treatment of concerted proton-electron transfer.

SUBMITTER: Coste SC

PROVIDER: S-EPMC8513817 | biostudies-literature | 2021 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

C-H oxidation in fluorenyl benzoates does not proceed through a stepwise pathway: revisiting asynchronous proton-coupled electron transfer.

Coste Scott C SC Brezny Anna C AC Koronkiewicz Brian B Mayer James M JM

Chemical science 20210910 39

2-Fluorenyl benzoates were recently shown to undergo C-H bond oxidation through intramolecular proton transfer coupled with electron transfer to an external oxidant. Kinetic analysis revealed unusual rate-driving force relationships. Our analysis indicated a mechanism of multi-site concerted proton-electron transfer (MS-CPET) for all of these reactions. More recently, an alternative interpretation of the kinetic data was proposed to explain the unusual rate-driving force relationships, invoking ...[more]

PMID: 34745543

Similar Datasets

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.

Dataset Information

C-H oxidation in fluorenyl benzoates does not proceed through a stepwise pathway: revisiting asynchronous proton-coupled electron transfer.

Publications

C-H oxidation in fluorenyl benzoates does not proceed through a stepwise pathway: revisiting asynchronous proton-coupled electron transfer.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets