Preparation and properties of novel hetero-halogen complexes

Although hetero-halogen compounds are versatile synthetic intermediates, their one-step preparation methods are scarcely known. Herein, we describe the preparation of two novel air-stable hetero-halogen complexes, (DMI)2HBr2I and (DMI)2HCl2I (DMI: 1,3-dimethyl-2-imidazolidinone). These complexes were then reacted with alkenes and alkynes, affording hetero-halogen compounds such as bromoiodides and chloroiodides in one step. Iodoalkoxylation and iodolactonisation were also performed with these complexes. Air-stable IBr and ICl alternatives [Display omitted] •Novel air-stable hetero-halogen complexes, DIBI and DICI, were prepared.•Bromoiodination and chloroiodination were performed using these complexes.•Iodoalkoxylation and iodolactonisation were also carried out with the complexes.•Prepared DIBI worked better on bromoiodination of alkynes than other IBr sources.