Iodine(I) pnictogenate complexes as Iodination reagents

Halogen(I) complexes are widely used as halogenation reagents and traditionally feature homoleptic stabilising Lewis bases, though the recent revitalisation of iodine(I) carboxylate chemistry has provided isolable examples of heteroleptic iodine(I) complexes. This work reports iodine(I) pnictogenate complexes stabilised by a Lewis base (L), Ph₂P(O)O─I─L, synthesised via cation exchange from the silver(I) precursor, (Ph₂P(O)OAg)_n. The complexes were characterised in both solution (¹H, ¹H-¹⁵N HMBC, ³¹P) and the solid state, and supplemented computationally by DFT studies. Interestingly, these iodine(I) pnictogenates demonstrate a range of stabilities, and have been found to excel as iodination reagents in comparison to carbonyl hypoiodites, with comparable reactivity to the eponymous Barluenga’s reagent in the iodination of antipyrine.