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 considere

SUBMITTER: Karandikar SS 

PROVIDER: S-EPMC9172531 | biostudies-literature | 2022 Jun

REPOSITORIES: biostudies-literature