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Toward a reverse hierarchy of halogen bonding between bromine and iodine

Faraday Discussions publication by Emmanuel Aubert, Enrique Espinosa, Irène Nicolas, Olivier Jeannin and Marc Fourmigué in volume 203 Halogen Bonding in Supramolecular and Solid State Chemistry

We have indeed recently investigated non-symmetric structures where a very strong XB donor, namely N-iodosaccharin (NISac) is faced with electron-rich pyridines such as 4-picoline and 4-dimethylamino-pyridine (DMAP). We showed that NISac.DMAP could be actually better described under its ionic form, that is a saccharinate anion halogen bonded to the corresponding N-iodopyridinium , while the structural characteristics of the corresponding 4-picoline adduct, NISac.Pic, indicated a predominant neutral form. In order to evaluate the differences between iodine and bromine in such systems, we have investigated the nature of the N-bromosaccharin (NBSac) adducts with both 4-picoline and 4-dimethylaminopyridine. The isolation of a crystalline adduct of NBSac with 4-picoline allows now for a very informative comparison of the relative role of the halogen atom in these neutral/ionic halogen-bonded systems, as detailed in this paper.

DOI 10.1039/C7FD00067G
Faraday Discuss., 2017,203, 389-406