It is also easily and inexpensively synthesized by the oxidation of dirhenium decacarbonyl with bromine:[1] It was first prepared by the "reductive carbonylation" of rhenium(III) bromide:[2] Copper(I) bromide is a byproduct.

Bromopentacarbonylrhenium(I) is a precursor to other rhenium complexes.

It reacts with zinc and acetic acid to give pentacarbonylhydridorhenium (HRe(CO)5).

[3] It also reacts with tetraethylammonium bromide in diglyme to give [NEt4]2[ReBr3(CO)3)], an important precursor to compounds containing the rhenium tricarbonyl fragment.

[4] Heating bromopentacarbonylrhenium(I) in water give the triaquo complex: This route avoids the formation of the tetraethylammonium bromide byproduct, which is often difficult to remove from reaction mixtures.