We report a postfunctionalization synthetic route to dipyrrin complexes that gives access to a broad range of new complexes. This route involves the coordination of a 5-methylthiodipyrrinato ligand to a metal centre followed by displacement of the thiomethyl moiety by a nucleophile. Using rhenium(I) as a platform and amine nucleophiles, we show how complexes that would be difficult or impossible to synthesize via traditional methods can now be accessed.