Journal article
Electrostatically tuning radical addition and atom abstraction reactions with distonic radical ions
OJ Shiels, SC Brydon, BLJ Poad, DL Marshall, SD Houston, H Xing, PV Bernhardt, GP Savage, CM Williams, DG Harman, BB Kirk, G da Silva, SJ Blanksby, AJ Trevitt
Chemical Science | ROYAL SOC CHEMISTRY | Published : 2025
DOI: 10.1039/d4sc06333c
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 whic..
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Grants
Awarded by Queensland University of Technology
Funding Acknowledgements
The authors acknowledge access and training on advanced instrumentation through the Central Analytical Research Facility (CARF) at the Queensland University of Technology. A. J. T., G. d. S. and S. J. B. acknowledge financial support for this research from the Australian Research Council (ARC) through the Discovery Project scheme (DP170101596 and DP240100612). The authors also acknowledge the generous allocation of computing resources by the NCI National Facility (Canberra, Australia) under Merit Allocation Scheme. In addition, the authors thank The University of Queensland (UQ) and the Commonwealth Scientific and Industrial Research Organisation (CSIRO, Melbourne) for financial support. The Australian Research Council for a Future Fellowship award (FT110100851) to C. M. W. is also gratefully acknowledged. S. D. H. gratefully acknowledges the Northcote Trust and Britain-Australia Society for their award of the Northcote Graduate Scholarship.