Electrochemical oxidation of aliphatic carboxylates: Kinetics, thermodynamics, and evidence for a shift from a concerted to a stepwise mechanism in the presence of water

• Main Author: Abdel Latif, Marwa K.
• Other Authors: Chemistry
• Format: Others
• Published: Virginia Tech 2018
• Subjects: convolution voltammetry; dissociative electron transfer; aliphatic carboxylates; aryl carboxylates; oxidation potential; hydrogen bonding; shift from concerted to stepwise; radical stabilization
• Online Access: http://hdl.handle.net/10919/82522

The mechanism and the oxidation potential of the dissociative single electron transfer for tetra-n-butylammonium acetate has been investigated via conventional (cyclic voltammetry) and convolution voltammetry. The oxidation potential for tetra-n-butylammonium acetate was determined to be 0.60 ± 0.10 (vs. Ag/ (0.1 M) AgNO3) in anhydrous acetonitrile. The results also indicated the mechanism of oxidation was concerted dissociative electron transfer (cDET), rather than stepwise as was previously reported. To further investigate the mechanism, a series of aliphatic and aromatic tetra-n butylammonium carboxylates were synthesized and investigated via convolution and conventional methods under anhydrous conditions (propionate, pivalate, phenyl acetate, and benzoate). The reported results showed high reproducibility and consistency with a concerted dissociative electron transfer for aliphatic carboxylates with a systematic shift in the oxidation potentials (0.60 ± 0.09 V for acetate, 0.47 ± 0.05 V for propionate, and 0.40 ± 0.05 V for pivalate) within the series which is expected trend based on radical stabilization energies of the alkyl groups on the aliphatic carboxylates. Hydrogen bonding was investigated as a possible source for the discrepancy between our results and the reported mechanism of the dissociative electron transfer. Because of the extreme hygroscopic nature of carboxylate salts, it was hypothesized that the presence of small amounts of water might alter the reaction mechanism. Deionized water and deuterium oxide additions to anhydrous acetonitrile were performed to test this hypothesis. The mechanism was noted to shift towards a stepwise mechanism as water was added. In addition, the derived oxidation potentials became more positive with increasing concentrations of water. Several explanations are presented with regards to water effects on the shift in the electron transfer mechanism. Indirect electrolysis (homogeneous redox catalysis) was also employed as an alternative and independent approach to quantify the oxidation potentials of carboxylates. A series of substituted ferrocenes were investigated as mediators for the oxidation of tetra-n-butylammonium acetate. Preliminary data showed redox catalysis was feasible for these systems. Further analyses of the electrochemical results suggested a follow-up chemical step (addition to mediator) that competes with the redox catalysis mechanism. As predicted from theoretical working curves, a plateau region in the ip/ipd plots (where no meaningful kinetic information could be obtained) was observed. Products mixture analyses verified the consumption of the mediator upon electrolysis, but no further information with regards to the nature of the mechanism was deduced. In a related study the effects of hydrogen bonding and ions on the reactivity of neutral free radicals were examined by laser flash photolysis. The rate of the β-scission of the cumyloxyl radical is influenced by cations (Li+ > Mg2+ ≈ Na+ > nBu4N+) due to stabilizing ion-dipole interactions in the transition state of the developing carbonyl group. Experimental findings are in a good agreement with theoretical work suggesting metal ion complexation can cause radical clocks to run fast with a more significant effect if there is an increase in dipole moment going from the reactant to the transition state. === Ph. D.