Chemistry Commons^™

Orbital Analysis Of Bonding In Diarylhalonium Salts And Relevance To Periodic Trends In Structure And Reactivity, Shubhendu S. Karandikar, Avik Bhattacharjee, Bryan Metze, Nicole Javaly, Edward J. Valente, Theresa M. Mccormick, David R. Stuart

Chemistry Faculty Publications and Presentations

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 …