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

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2022-03-21
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Chatterjee, Puranjan
Wang, Hsin
Manzano, J. Sebastián
Kanbur, Uddhav
Sadow, Aaron D.
Slowing, Igor
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Iowa State University Digital Repository, Ames IA (United States)
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Sadow, Aaron
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Slowing, Igor
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Chemistry

The Department of Chemistry seeks to provide students with a foundation in the fundamentals and application of chemical theories and processes of the lab. Thus prepared they me pursue careers as teachers, industry supervisors, or research chemists in a variety of domains (governmental, academic, etc).

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The Department of Chemistry was founded in 1880.

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Ames National Laboratory

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For more than 70 years, the Ames National Laboratory has successfully partnered with Iowa State University, and is unique among the 17 DOE laboratories in that it is physically located on the campus of a major research university. Many of the scientists and administrators at the Laboratory also hold faculty positions at the University and the Laboratory has access to both undergraduate and graduate student talent.

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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.
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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.
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