Diarylhalonium species are novel arylating agents that are typified by the heaviest known member - diaryliodonium salts. In the literature they are generally referred to as hypervalent and the three-center, four-electron (3c-4e) bonding model is most commonly employed to rationalize both structure and reactivity. Here, we use a combination of X-ray structure data and DFT to provide a refined bonding model that incorporates Bent's rule of fractional hybridization to account for deviations from the expected 90° C-E-C bond angle. This approach accurately predicts the structure for a wide range of isoelectronic molecules in which the central atom is from Group 16 (chalcogen) and 17 (halogen) of the p-block and does not rely on participation in a hypervalent bond. This refined bonding model will also form the basis for rationalizing and predicting reactivity trends among the diarylhalonium series.

Through the lens of Bent's rule: A refined bonding model to describe trends in structure and reactivity of diarylhalonium and related compounds

ACS Fall 2021

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