Catalytic Oxidation of Alcohol via Nickel Phosphine Complexes with Pendant Amines

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• 作者：Charles J. Weiss ; Parthapratim Das ; Deanna L. Miller ; Monte L. Helm ; Aaron M. Appel
• 刊名：ACS Catalysis
• 出版年：2014
• 出版时间：September 5, 2014
• 年：2014
• 卷：4
• 期：9
• 页码：2951-2958
• 全文大小：384K
• ISSN：2155-5435

文摘

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 and 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.

Keywords:

alcohol oxidation; nickel; electrochemistry; catalysis; proton relay