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

File

2022-SadowAaron-SurfaceLigands.pdf (1.5 MB)

Date

2022-02-04

Authors

Chatterjee, Puranjan
Wang, Hsin
Manzano, J. Sebastián
Kanbur, Uddhav
Sadow, Aaron D.
Slowing, Igor

Publisher

Royal Society of Chemistry

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Organizational Units

Chemistry

Organizational Unit

Ames Laboratory

Organizational Unit

Department

ChemistryAmes Laboratory

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.

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.