Selective Hydrogenation of Azobenzene to Hydrazobenzene Via Proton-Coupled Electron Transfer from a Polyoxotungstate Cluster

Overview

Journal JACS Au

Publisher American Chemical Society

Specialty Chemistry

Date 2024 Apr 26

PMID 38665657

Authors

Zhou Lu

Shannon E Cooney

James R McKone

Ellen M Matson

Affiliations

Soon will be listed here.

Abstract

In this report, we describe proton-coupled electron transfer (PCET) reactivity at the surface of the Keggin-type polyoxotungstate cluster [BuN][PWO] () in acetonitrile. Bond dissociation free energies (BDFEs) of the O-H groups generated upon reduction of in the presence of acid are determined through the construction of a potential-p diagram. The surface O-H bonds are found to be weak (BDFE(O-H) < 48 kcal mol), comparable to the BDFE of H. This is consistent with the observed formation of H upon addition of a suitably strong organic acid, HNPh (p = 5.98), to the reduced form of the cluster. The one-electron reduced form of is isolated and used in conjunction with acid to realize the stoichiometric semihydrogenation of azobenzene via PCET from the surface of the reduced cluster.

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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

Bezdek M, Guo S, Chirik P . Coordination-induced weakening of ammonia, water, and hydrazine X-H bonds in a molybdenum complex. Science. 2016; 354(6313):730-733. DOI: 10.1126/science.aag0246. View

Miu E, Mpourmpakis G, McKone J . Predicting the Energetics of Hydrogen Intercalation in Metal Oxides Using Acid-Base Properties. ACS Appl Mater Interfaces. 2020; 12(40):44658-44670. DOI: 10.1021/acsami.0c11300. View

Artz J, Muller T, Thenert K, Kleinekorte J, Meys R, Sternberg A . Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment. Chem Rev. 2017; 118(2):434-504. DOI: 10.1021/acs.chemrev.7b00435. View

Proe K, Schreiber E, Matson E . Proton-Coupled Electron Transfer at the Surface of Polyoxovanadate-Alkoxide Clusters. Acc Chem Res. 2023; 56(12):1602-1612. PMC: 10286311. DOI: 10.1021/acs.accounts.3c00166. View

Mayer J . Bonds over Electrons: Proton Coupled Electron Transfer at Solid-Solution Interfaces. J Am Chem Soc. 2023; 145(13):7050-7064. PMC: 10080693. DOI: 10.1021/jacs.2c10212. View

MOZINGO R . Palladium catalysts. Organic Synth. 2010; 26:77-82. DOI: 10.1002/0471264180.os026.23. View

Park Y, Kim S, Tian L, Zhong H, Scholes G, Chirik P . Visible light enables catalytic formation of weak chemical bonds with molecular hydrogen. Nat Chem. 2021; 13(10):969-976. DOI: 10.1038/s41557-021-00732-z. View

Lv H, Guo W, Wu K, Chen Z, Bacsa J, Musaev D . A noble-metal-free, tetra-nickel polyoxotungstate catalyst for efficient photocatalytic hydrogen evolution. J Am Chem Soc. 2014; 136(40):14015-8. DOI: 10.1021/ja5084078. View

10.

Zubar V, Dewanji A, Rueping M . Chemoselective Hydrogenation of Nitroarenes Using an Air-Stable Base-Metal Catalyst. Org Lett. 2021; 23(7):2742-2747. PMC: 8041384. DOI: 10.1021/acs.orglett.1c00659. View

11.

Zhang L, Zhou M, Wang A, Zhang T . Selective Hydrogenation over Supported Metal Catalysts: From Nanoparticles to Single Atoms. Chem Rev. 2019; 120(2):683-733. DOI: 10.1021/acs.chemrev.9b00230. View

12.

Fertig A, Matson E . Connecting Thermodynamics and Kinetics of Proton Coupled Electron Transfer at Polyoxovanadate Surfaces Using the Marcus Cross Relation. Inorg Chem. 2022; 62(5):1958-1967. PMC: 9906739. DOI: 10.1021/acs.inorgchem.2c02541. View

13.

Zhu Y, DU Z, Wang J, Yang J, Mei H, Xu Y . Efficient Visible-Light-Driven Hydrogen Production over Cu-Modified Polyoxotungstate Hybrids. Inorg Chem. 2022; 61(50):20397-20404. DOI: 10.1021/acs.inorgchem.2c03028. View

14.

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

15.

Niu Z, Zhang W, Lan P, Aguila B, Ma S . Promoting Frustrated Lewis Pairs for Heterogeneous Chemoselective Hydrogenation via the Tailored Pore Environment within Metal-Organic Frameworks. Angew Chem Int Ed Engl. 2019; 58(22):7420-7424. DOI: 10.1002/anie.201903763. View

16.

Qiu Y, Ray D, Yan L, Li X, Song M, Engelhard M . Proton Relay for the Rate Enhancement of Electrochemical Hydrogen Reactions at Heterogeneous Interfaces. J Am Chem Soc. 2023; 145(48):26016-26027. DOI: 10.1021/jacs.3c06398. View

17.

Cooney S, Fertig A, Buisch M, Brennessel W, Matson E . Coordination-induced bond weakening of water at the surface of an oxygen-deficient polyoxovanadate cluster. Chem Sci. 2022; 13(43):12726-12737. PMC: 9645371. DOI: 10.1039/d2sc04843d. View

18.

Zhang W, Qin R, Fu G, Zheng N . Hydrogen Bond Network Induced by Surface Ligands Shifts the Semi-hydrogenation Selectivity over Palladium Catalysts. J Am Chem Soc. 2023; 145(18):10178-10186. DOI: 10.1021/jacs.3c00953. View

19.

Stephan D . Frustrated Lewis pairs: from concept to catalysis. Acc Chem Res. 2014; 48(2):306-16. DOI: 10.1021/ar500375j. View

20.

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