Journal article

Evidence that pi-ligand exchange reactions of chalcogen iranium ions proceed via Huckel pseudocoarctate transition states

Samuel C Brydon, Gabriel da Silva, Jonathan M White

Journal of Physical Organic Chemistry | Wiley | Published : 2020


Despite numerous computational and experimental studies on the π‐ligand exchange reactions of chalcogen iranium ions, a classification of the reaction class has yet to be made. The characteristics of the transition states presented thus far suggested a coarctate nature with two bonds breaking and forming simultaneously at the chalcogen centre. The change in barrier height, depending on the nature of the chalcogen and the alkene, was initially attributed as a shift in the degree of aromaticity moving from pseudocoarctate to coarctate reactions. However, this paper suggests that all 12 reactions under consideration are pseudocoarctate with a Hückel number of delocalised π electrons based on co..

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Funding Acknowledgements

We thank the Australian Government for a Research Training Program (RTP) scholarship to SB. The DFT calculations were performed on the Spartan High Performance Computing (HPC) System hosted by the Research Platform Services at the University of Melbourne.[66] Thanks to Fynn Roehricht from the Herges research group for help in setting up the ACID program. ACID calculations were conducted on the Argali HPC Service provided by the Melbourne School of Engineering hosted at the University of Melbourne.