Voltammetric and electrochemical ESR studies of oxidation reactions mediated by tris(4-bromophenyl)amine in acetonitrile.
The electrochemical oxidation of tris(4-bromophenyl)amine in the presence of 2,6-lutidine is examined in acetonitrile. Voltammetric and spectroscopic investigations suggest that the electrogenerated triaryl aminium radical cation oxidizes 2,6-lutidine in an EC' mechanism, and an equilibrium constant for this homogeneous electron transfer is estimated. The mediated oxidation of a protected phenyl selenoglycoside by this reaction mixture is studied by the use of electrochemical ESR, employing a tubular flow cell, and signal intensity data is found to be consistent with the proposed mechanism, allowing the determination of kinetic parameters by computational simulation. Products of the mediated glycoside oxidation are determined by proton NMR and mass spectrometry.
Wain
Andrew J
AJ
Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford OX1 3QZ, UK
Streeter
Ian
I
Thompson
Mary
M
Fietkau
Nicole
N
Drouin
Ludovic
L
Fairbanks
Antony J
AJ
Compton
Richard G
RG
D000097:Acetonitriles / Q000737:chemistry*; D004563:Electrochemistry; D004566:Electrodes; D004578:Electron Spin Resonance Spectroscopy / Q000379:methods; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D000644:Quaternary Ammonium Compounds / Q000737:chemistry*; D012680:Sensitivity and Specificity; D013056:Spectrophotometry, Ultraviolet / Q000379:methods
D000097:Acetonitriles; D009942:Organometallic Compounds; D000644:Quaternary Ammonium Compounds; C079938:tris(4-bromophenyl)ammoniumyl hexachloroantimonate; C032159:acetonitrile