2024-06-21T14:52:52 n27693

Electrostatically tuning radical addition and atom abstraction reactions with distonic radical ions

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This data set accompanies the manuscript "Electrostatically tuning radical addition and atom abstraction reactions with distonic radical ions" by Oisin J. Shiels and Samuel C. Brydon, Berwyck L. J. Poad, David L. Marshall, Sevan D. Houston, Hui Xing, Paul V. Bernhardt, G. Paul Savage, Craig M. Williams, David G. Harman, Benjamin B. Kirk, Gabriel da Silva, Stephen J. Blanksby and Adam J. Trevitt (submitted to Chemical Science).

Abstract: Although electrostatic catalysis can enhance the kinetics and selectivity of reactions to produce greener synthetic processes, the highly directional nature of electrostatic interactions has limited widespread application. In this study, the influence of oriented electric fields (OEF) on radical addition and atom abstraction reactions are systematically explored with ion-trap mass spectrometry using structurally diverse distonic radical ions that maintain spatially separated charge and radical moieties. When installed on rigid molecular scaffolds, charged functional groups lock the magnitude and orientation of the internal electric field with respect to the radical site, creating an OEF which tunes the reactivity across the set of gas-phase carbon-centred radical reactions. In the first case, OEFs predictably accelerate and decelerate the rate of molecular oxygen addition to substituted phenyl, adamantyl, and cubyl radicals, depending on the polarity of the charged functional group and dipole orientation. In the second case, OEFs modulate competition between chlorine and hydrogen atom abstraction from chloroform based on interactions between charge polarity, dipole orientation, and radical polarizability. Importantly, this means the same charge polarity can induce different changes to reaction selectivity. Quantum chemical calculations of these reactions with DSD-PBEP86-D3(BJ)/aug-cc-pVTZ show correlations between the barrier heights and the experimentally determined reaction kinetics. Field effects are consistent between phenyl and cubyl scaffolds, pointing to through-space rather than through-bond field effects, congruent with computations showing that the same effects can be mimicked by point charges. These results experimentally demonstrate how internal OEFs generated by carefully placed charged functional groups can systematically control radical reactions.

Data file includes: experimental mass spectra files from kinetic experiments and output files from Gaussian calculations.

Geographical area of data collection

kmlPolyCoords
153.467489,-27.021860 152.679693,-27.021860 152.679693,-27.660244 153.467489,-27.660244 153.467489,-27.021860

Research areas

Electric field
Kinetics
Density functional theory
Ion-molecule reaction
Chloroform
Gas-phase
Mass spectrometry
Radical addition

Cite this collection

Shiels, Oisin J.; Brydon, Samuel C.; Poad, Berwyck L. J.; Marshall, David L.; Houston, Sevan D.; Xing, Hui; Bernhardt, Paul V.; Savage, G. Paul; Williams, Craig M.; Harman, David G.; Kirk, Benjamin B.; da Silva, Gabriel; Blanksby, Stephen J.; Trevitt, Adam J.; (2024): Electrostatically tuning radical addition and atom abstraction reactions with distonic radical ions. Queensland University of Technology. (Dataset) https://doi.org/10.25912/RDF_1718945540597

Partner institution

CSIRO Manufacturing https://www.csiro.au/
University of Queensland https://www.uq.edu.au/
The University of Melbourne https://www.unimelb.edu.au/
Western Sydney University https://www.westernsydney.edu.au/
University of Wollongong https://www.uow.edu.au/

Data file types

Data file types consist of mass spectra (.raw) files and Gaussian (.log) files

Licence


Creative Commons Attribution-NonCommercial-Share Alike 4.0 (CC-BY-NC-SA)
http://creativecommons.org/licenses/by-nc-sa/4.0/

Copyright

© Queensland University of Technology, 2024.

Connections

Has association with
Berwyck Poad  (Researcher)
David Marshall  (Researcher)
Has chief investigator
Stephen Blanksby  (Researcher)

Other

Date record created:
2024-06-04T14:20:53
Date record modified:
2024-06-21T14:52:52
Record status:
Published - Open Access