Surface ligands enhance the catalytic activity of supported Au nanoparticles for the aerobic α-oxidation of amines to amides

dc.contributor.author Chatterjee, Puranjan
dc.contributor.author Wang, Hsin
dc.contributor.author Manzano, J. Sebastián
dc.contributor.author Kanbur, Uddhav
dc.contributor.author Sadow, Aaron D.
dc.contributor.author Slowing, Igor
dc.contributor.author Sadow, Aaron
dc.contributor.author Slowing, Igor
dc.contributor.department Chemistry
dc.contributor.department Ames National Laboratory
dc.contributor.other Chemistry
dc.date.accessioned 2022-02-08T21:57:39Z
dc.date.available 2022-02-08T21:57:39Z
dc.date.issued 2022-03-21
dc.description.abstract The catalytic aerobic α-oxidation of amines in water is an atom economic and green alternative to current methods of amide synthesis. The reaction uses O2 as terminal oxidant, avoids hazardous reactants and gives water as the only byproduct. Here we report that the catalytic activity of silica-supported Au nanoparticles for the aerobic α-oxidation of amines can be improved by tethering pyridyl ligands to the support. In contrast, immobilization of thiol groups on the material gives activities comparable to Au supported on bare silica. Our studies indicate that the ligands affect the electronic properties of the Au nanoparticles and thereby determine their ability to activate O2 and mediate C-H cleavage in the amine substrate. The reaction likely proceeds via an Au catalyzed β-hydride elimination enabled by backdonation from electron-rich metal to the *C-H orbital. O2, which is also activated on electron-rich Au, acts as a scavenger to remove H from the metal surface and regenerate the active sites. The mechanistic understanding of the catalytic conversion led to a new approach for forming C-C bonds α to the N atoms of amines.
dc.description.comments This is a manuscript of an article published as Chatterjee, Puranjan, Hsin Wang, Juan Sebastian Manzano, Uddhav Kanbur, Aaron D. Sadow, and Igor Ivan Slowing. "Surface ligands enhance the catalytic activity of supported Au nanoparticles for the aerobic α-oxidation of amines to amides." Catalysis Science & Technology (2022). DOI: 10.1039/D1CY02121D. Copyright 2022 The Royal Society of Chemistry. Attribution-NonCommercial 4.0 International (CC BY-NC 4.0). Posted with permission. DOE Contract Number(s): AC02-07CH11358.
dc.identifier.other 1844444
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/dv6lgdmz
dc.language.iso en
dc.publisher Iowa State University Digital Repository, Ames IA (United States)
dc.relation.ispartofseries IS-J 10726
dc.source.uri https://doi.org/10.1039/D1CY02121D *
dc.subject.disciplines DegreeDisciplines::Engineering::Chemical Engineering::Catalysis and Reaction Engineering
dc.subject.disciplines DegreeDisciplines::Physical Sciences and Mathematics::Chemistry::Materials Chemistry
dc.title Surface ligands enhance the catalytic activity of supported Au nanoparticles for the aerobic α-oxidation of amines to amides
dc.type Article
dspace.entity.type Publication
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