A Solid-State Studyof the Influence of the LewisBase on Iodine(I) 4‑Trifluoromethylbenzoate Derivatives

A library of directly comparable iodine­(I) 4-trifluoromethylbenzoate derivatives, which only differ in the stabilizing Lewis bases incorporated, has been assembled. A total of 35 complexes with different Lewis bases were successfully crystallized and their structures determined by SCXRD. These structures encompass a variety of substituted pyridines (2-, 3-, 4-, and disubstituted), as well as for the first time 5-membered N-heterocycles including substituted imidazoles and triazoles. In addition, a wide range of previously untested functional groups have been investigated to probe the functional group tolerance of the iodine­(I) center, as well as the potential of these O–I–N complexes to be utilized in further synthetically useful chemical transformations with retention of the iodine­(I) center. This library of solid-state structures is also supported by DFT calculations on select examples, permitting further insights to be drawn between the relationship of Lewis basicity and the halogen bonding upon their incorporation into iodine­(I) carboxylates.