Connecting Thermodynamics and Kinetics of Proton Coupled Electron Transfer at Polyoxovanadate Surfaces Using the Marcus Cross Relation

Overview

Journal Inorg Chem

Specialty Chemistry

Date 2022 Sep 1

PMID 36049052

Authors

Alex A Fertig

Ellen M Matson

Affiliations

Soon will be listed here.

Abstract

Here, we evaluate the efficacy of multiple methods for elucidating the average bond dissociation free energy (BDFE) of two surface hydroxide moieties in a reduced polyoxovanadate cluster, [VO(OH)(TRIOL)]. Through cyclic voltammetry, individual thermochemical parameters describing proton coupled electron transfer (PCET) are obtained, without the need for synthetic isolation of intermediates. Further, we demonstrate that a method involving a series of open circuit potential measurements with varying ratios of reduced to oxidized clusters is most attractive for the direct measurement of BDFE(O-H) for polyoxovanadate clusters as this approach also determines the stoichiometry of PCET. We subsequently connect the driving force of PCET to the rate constant for the transfer of hydrogen atoms to a series of organic substrates through the Marcus cross relation. We show that this method is applicable for the prediction of reaction rates for multielectron/multiproton transfer reactions, extending the findings from previous work focused on single electron/proton reactions.

Citing Articles

Engineering mechanisms of proton-coupled electron transfer to a titanium-substituted polyoxovanadate-alkoxide.

Cooney S, Duggan S, Walls M, Gibson N, Mayer J, Miro P Chem Sci. 2025; 16(6):2886-2897.

PMID: 39822902 PMC: 11733765. DOI: 10.1039/d4sc06468b.

Vanadium Substitution Dictates H Atom Uptake at Lindqvist-type Polyoxotungstates.

Shiels D, Lu Z, Pascual-Borras M, Cajiao N, Marinho T, Brennessel W Inorg Chem. 2024; 63(49):23304-23316.

PMID: 39565382 PMC: 11632773. DOI: 10.1021/acs.inorgchem.4c03873.

Electrochemically Determined and Structurally Justified Thermochemistry of H atom Transfer on Ti-Oxo Nodes of the Colloidal Metal-Organic Framework Ti-MIL-125.

Gokce Altincekic N, Lander C, Roslend A, Yu J, Shao Y, Noh H J Am Chem Soc. 2024; 146(49):33485-33498.

PMID: 39479987 PMC: 11640761. DOI: 10.1021/jacs.4c10421.

Organofunctionalized borotungstate polyoxometalates as tunable photocatalysts for oxidative dimerization of amines.

Tsang N, Kibler A, Argent S, Lam H, Jones K, Newton G Chem Sci. 2024; .

PMID: 39170724 PMC: 11332656. DOI: 10.1039/d4sc03534h.

Tuning the Thermochemistry and Reactivity of a Series of Cu-Based 4H/4e Electron-Coupled-Proton Buffers.

Wu T, Puri A, Qiu Y, Ye D, Sarma R, Wang Y Inorg Chem. 2024; 63(20):9014-9025.

PMID: 38723621 PMC: 11110016. DOI: 10.1021/acs.inorgchem.4c00835.

References

Agarwal R, Coste S, Groff B, Heuer A, Noh H, Parada G . Free Energies of Proton-Coupled Electron Transfer Reagents and Their Applications. Chem Rev. 2021; 122(1):1-49. PMC: 9175307. DOI: 10.1021/acs.chemrev.1c00521. View

McCarthy B, Dempsey J . Decoding Proton-Coupled Electron Transfer with Potential-pK Diagrams. Inorg Chem. 2017; 56(3):1225-1231. DOI: 10.1021/acs.inorgchem.6b02325. View

Fertig A, Brennessel W, McKone J, Matson E . Concerted Multiproton-Multielectron Transfer for the Reduction of O to HO with a Polyoxovanadate Cluster. J Am Chem Soc. 2021; 143(38):15756-15768. DOI: 10.1021/jacs.1c07076. View

Warren J, Mayer J . Predicting organic hydrogen atom transfer rate constants using the Marcus cross relation. Proc Natl Acad Sci U S A. 2010; 107(12):5282-7. PMC: 2851756. DOI: 10.1073/pnas.0910347107. View

Agarwal R, Kim H, Mayer J . Nanoparticle O-H Bond Dissociation Free Energies from Equilibrium Measurements of Cerium Oxide Colloids. J Am Chem Soc. 2021; 143(7):2896-2907. DOI: 10.1021/jacs.0c12799. View

Long D, Burkholder E, Cronin L . Polyoxometalate clusters, nanostructures and materials: from self assembly to designer materials and devices. Chem Soc Rev. 2006; 36(1):105-21. DOI: 10.1039/b502666k. View

Fertig A, Rabbani S, Koch M, Brennessel W, Miro P, Matson E . Physicochemical implications of surface alkylation of high-valent, Lindqvist-type polyoxovanadate-alkoxide clusters. Nanoscale. 2021; 13(12):6162-6173. DOI: 10.1039/d0nr09201k. View

Yu H, Yang Y, Zhang L, Dang Z, Hu G . Quantum-chemical predictions of pKa's of thiols in DMSO. J Phys Chem A. 2014; 118(3):606-22. DOI: 10.1021/jp410274n. View

Rountree E, McCarthy B, Dempsey J . Decoding Proton-Coupled Electron Transfer with Potential-p K Diagrams: Applications to Catalysis. Inorg Chem. 2019; 58(10):6647-6658. DOI: 10.1021/acs.inorgchem.8b03368. View

10.

Schreiber E, Fertig A, Brennessel W, Matson E . Oxygen-Atom Defect Formation in Polyoxovanadate Clusters via Proton-Coupled Electron Transfer. J Am Chem Soc. 2022; 144(11):5029-5041. PMC: 8949770. DOI: 10.1021/jacs.1c13432. View

11.

Misra A, Kozma K, Streb C, Nyman M . Beyond Charge Balance: Counter-Cations in Polyoxometalate Chemistry. Angew Chem Int Ed Engl. 2019; 59(2):596-612. PMC: 6972580. DOI: 10.1002/anie.201905600. View

12.

Wise C, Agarwal R, Mayer J . Determining Proton-Coupled Standard Potentials and X-H Bond Dissociation Free Energies in Nonaqueous Solvents Using Open-Circuit Potential Measurements. J Am Chem Soc. 2020; 142(24):10681-10691. DOI: 10.1021/jacs.0c01032. View

13.

Wise C, Mayer J . Electrochemically Determined O-H Bond Dissociation Free Energies of NiO Electrodes Predict Proton-Coupled Electron Transfer Reactivity. J Am Chem Soc. 2019; 141(38):14971-14975. DOI: 10.1021/jacs.9b07923. View

14.

Soetbeer J, Dongare P, Hammarstrom L . Marcus-type driving force correlations reveal the mechanism of proton-coupled electron transfer for phenols and [Ru(bpy)] in water at low pH. Chem Sci. 2018; 7(7):4607-4612. PMC: 6013771. DOI: 10.1039/c6sc00597g. View

15.

Shi R, Tessensohn M, Lauw S, Foo N, Webster R . Tuning the reduction potential of quinones by controlling the effects of hydrogen bonding, protonation and proton-coupled electron transfer reactions. Chem Commun (Camb). 2019; 55(16):2277-2280. DOI: 10.1039/c8cc09188a. View

16.

Song Y, Tsunashima R . Recent advances on polyoxometalate-based molecular and composite materials. Chem Soc Rev. 2012; 41(22):7384-402. DOI: 10.1039/c2cs35143a. View

17.

Warburton R, Soudackov A, Hammes-Schiffer S . Theoretical Modeling of Electrochemical Proton-Coupled Electron Transfer. Chem Rev. 2022; 122(12):10599-10650. DOI: 10.1021/acs.chemrev.1c00929. View

18.

Prins R . Hydrogen spillover. Facts and fiction. Chem Rev. 2012; 112(5):2714-38. DOI: 10.1021/cr200346z. View

19.

Lopez X, Bo C, Poblet J . Electronic properties of polyoxometalates: electron and proton affinity of mixed-addenda Keggin and Wells-Dawson anions. J Am Chem Soc. 2002; 124(42):12574-82. DOI: 10.1021/ja020407z. View

20.

Amtawong J, Skjelstad B, Balcells D, Don Tilley T . Concerted Proton-Electron Transfer Reactivity at a Multimetallic CoO Cubane Cluster. Inorg Chem. 2020; 59(20):15553-15560. DOI: 10.1021/acs.inorgchem.0c02625. View