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

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. Physical Sciences Division, Pacific Northwest National Laboratory, P.O. Box 999, MS K2-57, Richland, Washington 99352, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1386171
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: ACS Catalysis; Journal Volume: 4; Journal Issue: 9; Related Information: CME partners with Pacific Northwest National Laboratory (lead); University of Illinois, Urbana-Champaign; Pennsylvania State University; University of Washington; University of Wyoming
Country of Publication:
United States
Language:
English
Subject:
catalysis (homogeneous), catalysis (heterogeneous), solar (fuels), bio-inspired, energy storage (including batteries and capacitors), hydrogen and fuel cells, charge transport, materials and chemistry by design, synthesis (novel materials)

Citation Formats

Weiss, Charles J., Das, Parthapratim, Miller, Deanna L., Helm, Monte L., and Appel, Aaron M. Catalytic Oxidation of Alcohol via Nickel Phosphine Complexes with Pendant Amines. United States: N. p., 2014. Web. doi:10.1021/cs500853f.
Weiss, Charles J., Das, Parthapratim, Miller, Deanna L., Helm, Monte L., & Appel, Aaron M. Catalytic Oxidation of Alcohol via Nickel Phosphine Complexes with Pendant Amines. United States. doi:10.1021/cs500853f.
Weiss, Charles J., Das, Parthapratim, Miller, Deanna L., Helm, Monte L., and Appel, Aaron M. Fri . "Catalytic Oxidation of Alcohol via Nickel Phosphine Complexes with Pendant Amines". United States. doi:10.1021/cs500853f.
@article{osti_1386171,
title = {Catalytic Oxidation of Alcohol via Nickel Phosphine Complexes with Pendant Amines},
author = {Weiss, Charles J. and Das, Parthapratim and Miller, Deanna L. and Helm, Monte L. and Appel, Aaron M.},
abstractNote = {},
doi = {10.1021/cs500853f},
journal = {ACS Catalysis},
number = 9,
volume = 4,
place = {United States},
year = {Fri Aug 01 00:00:00 EDT 2014},
month = {Fri Aug 01 00:00:00 EDT 2014}
}
  • 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 oxidationmore » 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 multiprogram national laboratory operated for DOE by Battelle.« less
  • Nickel phosphine complexes with pendant amines have been found to be electrocatalysts for the oxidation of primary and secondary alcohols, with turnover frequencies as high as 3.3 s-1. These complexes are the first electrocatalysts for alcohol oxidation based on non-precious metals, which will be critical for use in fuel cells. The research by CJW, ESW, and AMA was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. The research by JASR was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center fundedmore » by the U.S. Department of Energy, Office of Science. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less
  • Nickel phosphine complexes with pendant amines are reported as the first nonprecious metal molecular electrocatalysts for the oxidation of alcohols.