DFT study of the oxidation of primary alcohols by TEMPO+ cation in presence of NaCO3- buffer: deprotonation/cyclic intermediate pathway

Data to support article:

Hydrodynamic Rocking Disc Electrode Study of EC’-Type TEMPO-Mediated Primary Alcohol Oxidations

DOI: 10.6084/m9.figshare.3079966

Journal: Electroanalysis

Authors:

Sunyhik D. Ahn ^a, Adrian C. Fisher ^b, Antoine Buchard ^a,
Steven D. Bull ^a, Alan M. Bond ^c, and Frank Marken*^a

 ^a Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK

^b Department of Chemical Engineering, University of Cambridge, New Museums Site, Pembroke Street, Cambridge, CB2 3RA, UK

^c Monash University, School of Chemistry, Clayton, Vic 3800, Australia

DFT study:

- The DFT optimised geometries and computed free enthalpies of various primary alcohols and aldehydes was used to calculate the thermodynamics of the oxidation reaction of various primary alcohols in presence of TEMPO+ cation and NaCO3- anion.

- The thermodynamics of formation of a cyclic intermediate formed by attack of an alkoxide on the nitrogen of the TEMPO⁺ cation was also calculated. 

- Transition states for the deprotonation step as well as the hydride transfer from the cyclic intermediate were also calculated and used to calculate the related activation barriers for each alcohols.

 

Protocol: rB3LYP/6-311+G(d,p)/cpcm=water/T=298.15K

 

Content:

- Gaussian09 rev A.02 output files