Halogen bonding and mechanochemistry combined: synthesis, characterization, and application of N-iodosaccharin pyridine complexes

Abstract

Triturating N-iodosaccharin with electron-donating 4-substituted pyridines leads to either charge-neutral XB or cationic iodine(i) complexes, offering promising alternatives to the ubiquitous Barluenga's reagent as electrophilic iodination reagents.

Iodine(I) pnictogenate complexes as Iodination reagents

“…The reactivity of 1b – 1g as potential iodination reagents was also of particular interest, given that they represented a distinctly-different motif compared to prior O─I─N complexes primarily based on iodine(I) carboxylates (RC(O)O─I─L; L = Lewis base), in both the hybridisation and electronegativity of the oxygen-adjacent substituent (with sp 3 P versus sp 2 C). The utility of antipyrine’s straightforward conversion to iodo-antipyrine has been previously demonstrated 41 , 62 , 63 and provides a useful benchmark in quantifying the reactivity of these iodine(I) phosphinates. The main limitation found for 1b – 1g was an inability to isolate and purify the bulk quantities necessary to proceed with such reactivity tests, with only 1d and 1f being found amenable.…”

The atypical solubility of silver(i) pentafluorobenzoate and its use as a catch-and-release agent

“…The solid-state structures of the natural-product adducts of 1 tested herein demonstrated excellent crystallographic metrics, which were found to have improved outcomes compared to those from other methodologies like encapsulation. Just as mechanochemical techniques minimise environmental impact by circumventing the use of toxic solvents like CH 2 Cl 2 , 50–52 the recovery and reuse of crystallisation materials, as demonstrated with 1 herein, could offer an environmentally-friendly alternative when attempting to prepare suitable crystals for SCXRD.…”

Fluoro and Trifluoromethyl Benzoyl Hypoiodite Complexes with Substituted Pyridines

“…[3][4][5] These properties have directly contributed to halogen bonding being utilised in a myriad of applications including the self-assembly of supramolecular architectures, [6][7][8][9] and even the recent development of generating such species in an environmentally-friendly fashion via mechanochemical methods. [10] Halogen bonding is defined as the interaction between the electrophilic region of a halogen atom and a neutral or anionic nucleophile. [11] The terminal example of halogen bonding is the complete ionisation of a halogen atom to a formally 1 + oxidation state, X + (X = Cl, Br, I), stabilised by a pair of Lewis bases (L).…”