Homogeneous electron-transfer reaction between electrochemically generated ferrocenium ions and amine-containing compounds

Torriero, Angel A. J., Shiddiky, Muhammad J. A., Burgar, Iko and Bond, Alan M. (2013) Homogeneous electron-transfer reaction between electrochemically generated ferrocenium ions and amine-containing compounds. Organometallics, 32 20: 128-136. doi:10.1021/om4002318


Author Torriero, Angel A. J.
Shiddiky, Muhammad J. A.
Burgar, Iko
Bond, Alan M.
Title Homogeneous electron-transfer reaction between electrochemically generated ferrocenium ions and amine-containing compounds
Journal name Organometallics   Check publisher's open access policy
ISSN 0276-7333
1520-6041
Publication date 2013-04-30
Year available 2013
Sub-type Article (original research)
DOI 10.1021/om4002318
Open Access Status Not Open Access
Volume 32
Issue 20
Start page 128
End page 136
Total pages 9
Place of publication Washington, DC, United States
Publisher American Chemical Society
Language eng
Formatted abstract
The homogeneous catalytic oxidation of propylamine (PrA), diethylamine (DEA), pyrrolidine (Pyr), and triethylamine (TEA) has been investigated for the first time in the presence of electrochemically generated ferrocenium ions as the catalyst. Mechanistic details for this electrocatalytic process have been investigated by cyclic voltammetry and other electrochemical techniques. A one-electron oxidative process was observed for all amines. Deviation from this mechanism was only  observed during controlled-potential bulk electrolysis of ferrocene in the presence of high concentrations of propylamine, where problems with electrode fouling and catalyst deactivation processes were encountered. The catalytic efficiency and the catalytic oxidation rate constants were estimated and found to follow the order TEA > Pyr > DEA > PrA. Interestingly, the catalytic reaction was not observed when ferrocene was replaced by decamethylferrocene. This observation was analyzed in terms of thermodynamic and structural effects, and a hypothesis is presented. The homogeneous catalytic oxidation reported opens a new avenue to achieve simple, low-cost, and efficient amine oxidation, which is potentially useful in several areas of chemistry.
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ
Additional Notes Published online April 30, 2013

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2014 Collection
Australian Institute for Bioengineering and Nanotechnology Publications
 
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Created: Sun, 05 May 2013, 05:33:18 EST by Dr Muhammad J. A. Shiddiky on behalf of Aust Institute for Bioengineering & Nanotechnology