An experimental, computational, and uncertainty analysis study of the rates of iodoalkane trapping by DABCO in solution phase organic media

• Published in: Physical chemistry chemical physics : PCCP Vol. 25; no. 9; pp. 6914 - 6926
• Main Authors: Grubel, Katarzyna, Rosenthal, W Steven, Autrey, Tom, Henson, Neil J, Koh, Katherine, Flowers, Sarah, Blake, Thomas A
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 01.03.2023; Royal Society of Chemistry (RSC)
• Subjects: Acetonitrile; Enthalpy; Heat of reaction; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Markov chains; NMR spectroscopy; Parameters; Substitution reactions; Uncertainty analysis
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d2cp05286e

NMR spectroscopy was used to measure the rates of the first and second substitution reactions between iodoalkane (R = Me, 1-butyl) and DABCO in methanol, acetonitrile and DMSO. Most of the reactions were recorded at three different temperatures, which permitted calculation of the activation parameters from Eyring and Arrhenius plots. Additionally, the reaction rate and heat of reaction for 1-iodobutane + DABCO in acetonitrile and DMSO were also measured using calorimetry. To help interpret experimental results, calculations were performed on the reactant, product, and transition state entities to understand structures, reaction enthalpies and activation parameters. Markov chain Monte Carlo statistical sampling was used to determine a distribution of kinetic rates with respect to the uncertainties in measured concentrations and correlations between parameters imposed by a kinetics model. The reactions with 1-iodobutane are found to be slower in all cases compared to reactions under similar conditions for iodomethane. This is due to steric crowding around the reaction centre for the larger butyl group compared to methyl which results in a larger activation energy for the reaction.