Journal article
Experimental and theoretical investigations into the mechanisms of haliranium ion π-ligand exchange reactions with cyclic alkenes in the gas phase
SC Brydon, G Da Silva, RAJ Ohair, JM White
Physical Chemistry Chemical Physics | Published : 2021
DOI: 10.1039/d1cp04494j
Abstract
Haliranium ions are intermediates often involved in complex cyclisations, where their structure allows for control over stereospecific outcomes. Extending previous studies into their structure and reactivity in the gas phase, this work focuses on the bimolecular reactivity of ethyl bromiranium and iodiranium ions with cyclic alkenes. The products observed via mass spectrometry were broadly attributed to either addition by cyclohexene at the iranium carbon or attack at the heteroatom to undergo associative π-ligand exchange. The model proposed was supported by both kinetic experiments and DFT calculations, where the rate of parent ion consumption proceeded at the collision rate (Br: k2 = 1.25..
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Awarded by Australian Government
Funding Acknowledgements
We thank the Australian Research Council (ARC) for financial support through the Discovery Projects (DP180101187 to RAJO) and the Australian Government for a Research Training Program (RTP) scholarship to SB. Calculations were performed on the Spartan High Performance Computing (HPC) System,<SUP>106</SUP> hosted by the Research Platform Services, and on the Argali HPC Service, provided by the Melbourne School of Engineering, at the University of Melbourne. Thanks to Howard Ma for performing the ion-molecule calibration experiments and many helpful discussions. Thanks to Dr Lars Goerigk and Dominique Wappett for assistance with Orca and other computational discussions.