Issue 22, 2022

Orbital analysis of bonding in diarylhalonium salts and relevance to periodic trends in structure and reactivity

Abstract

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.

Graphical abstract: Orbital analysis of bonding in diarylhalonium salts and relevance to periodic trends in structure and reactivity

Supplementary files

Article information

Article type
Edge Article
Submitted
03 Feb 2022
Accepted
10 May 2022
First published
19 May 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2022,13, 6532-6540

Orbital analysis of bonding in diarylhalonium salts and relevance to periodic trends in structure and reactivity

S. S. Karandikar, A. Bhattacharjee, B. E. Metze, N. Javaly, E. J. Valente, T. M. McCormick and D. R. Stuart, Chem. Sci., 2022, 13, 6532 DOI: 10.1039/D2SC02332F

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