AI Article Synopsis
- The report explores proton-coupled electron transfer (PCET) reactions occurring at the surface of the Keggin-type polyoxotungstate cluster [BuN][PWO] in acetonitrile.
- It determines the bond dissociation free energies (BDFEs) of the generated O-H groups and finds them to be weak, similar to the BDFE of hydrogen.
- The study demonstrates that using the one-electron reduced form of the cluster with a strong acid can efficiently semihydrogenate azobenzene through PCET.
Article 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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| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC11041919 | PMC |
| http://dx.doi.org/10.1021/jacsau.4c00127 | DOI Listing |
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