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Title: Catalytic Oxidation of Alcohol via Nickel Phosphine Complexes with Pendant Amines

Nickel complexes were prepared with diphosphine ligands that contain pendant amines, and these complexes catalytically oxidize primary and secondary alcohols to their respective aldehydes and ketones. Kinetic and mechanistic studies of these prospective electrocatalysts were performed to understand what influences the catalytic activity. For the oxidation of diphenylmethanol, the catalytic rates were determined to be dependent on the concentration of both the catalyst and the alcohol. The catalytic rates were found to be independent of the concentration of base and oxidant. The incorporation of pendant amines to the phosphine ligand results in substantial increases in the rate of alcohol oxidation with more electron-donating substituents on the pendant amine exhibiting the fastest rates. We thank Dr. John C. Linehan, Dr. Elliott B. Hulley, Dr. Jonathan M. Darmon, and Dr. Elizabeth L. Tyson for helpful discussions. Research by CJW, PD, DLM, and AMA was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Research by MLH was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. Pacific Northwest National Laboratory (PNNL) is a multiprogrammore » national laboratory operated for DOE by Battelle.« less
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Publication Date:
OSTI Identifier:
Report Number(s):
47453; KC0302010; KC0307010
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: ACS Catalysis, 4(9):2951-2958
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org:
Country of Publication:
United States
Environmental Molecular Sciences Laboratory