Iodine(I) and Silver(I) Complexes Incorporating 3-Substituted Pyridines

Building upon the first report of a 3-acetaminopyridine-based iodine(I) complex (1b) and its unexpected reactivity toward tBuOMe, several new 3-substituted iodine(I) complexes (2b–5b) have been synthesized. The iodine(I) complexes were synthesized from their analogous silver(I) complexes (2a–5a) via a silver(I) to iodine(I) cation exchange reaction, incorporating functionally related substituents as 3-acetaminopyridine in 1b; 3-acetylpyridine (3-Acpy; 2), 3-aminopyridine (3-NH2py; 3), and 3-dimethylaminopyridine (3-NMe2py; 4), as well as the strongly electron-withdrawing 3-cyanopyridine (3-CNpy; 5), to probe the possible limitations of iodine(I) complex formation. The individual properties of these rare examples of iodine(I) complexes incorporating 3-substituted pyridines are also compared to each other and contrasted to their 4-substituted counterparts which are more prevalent in the literature. While the reactivity of 1b toward etheric solvents could not be reproduced in any of the functionally related analogues synthesized herein, the reactivity of 1b was further expanded to a second etheric solvent. Reaction of bis(3-acetaminopyridine)iodine(I) (1b) and iPr2O gave [3-acetamido-1-(3-iodo-2-methylpentan-2-yl)pyridin-1-ium]PF6 (1d), which demonstrated potentially useful C–C and C–I bond formation under ambient conditions.