We acknowledge the National Science Foundation (NSF, CHE #1856705, CHE #1800599) for support of this work. SSK is grateful to the El-Mansy family for a summer fellowship at PSU. The NSF provided instrument funding for the BioAnalytical Mass Spectrometry Facility (MRI #1828753) and the high-performance computing cluster (DMS #1624776) at PSU, and the X-ray diffraction centre at the University of Portland (MRI #0604188).
Cyclic dibenzohalolium salts -- Research
Diarylhalonium compounds provide new opportunities as reagents and catalysts in the field of organic synthesis. The three center, four electron (3c–4e) bond is a center piece of their reactivity, but structural variation among the diarylhaloniums, and in comparison with other λ3-iodanes, indicates that the model needs refinement for broader applicability. We use a combination of Density Functional Theory (DFT), Natural Bond Orbital (NBO) Theory, and X-ray structure data to correlate bonding and structure for a λ3-iodane and a series of diarylchloronium, bromonium, and iodonium salts, and their isoelectronic diarylchalcogen counterparts. This analysis reveals that the s-orbital on the central halogen atom plays a greater role in the 3c–4e bond than previously considered. Finally, we show that our revised bonding model and associated structures account for both kinetic and thermodynamic reactivity for both acyclic phenyl(mesityl)halonium and cyclic dibenzohalolium salts.
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Karandikar, S. S., Bhattacharjee, A., Metze, B. E., Javaly, N., Valente, E. J., McCormick, T. M., & Stuart, D. R. (2022). Orbital analysis of bonding in diarylhalonium salts and relevance to periodic trends in structure and reactivity. Chemical Science.