The reaction of 5-amino-orotic acid (H 2 aor) with trans-[ReOBr 3 (PPh 3 ) 2 ] in 2-propanol produced the complex [Re V (apd)Br(aor)(PPh 3 ) 2 ] (1, apd 2− =5-imidopyrimidine-2,4-dione). The ligand apd 2− was formed by the decarboxylation of H 2 aor, and it is coordinated via the dinegative imido nitrogen only. The Schiff base derivative of H 2 aor, salicylimine-orotic acid {5-(2-hydroxy-benzylideneamino)-1,2,3,6-tetrahydro-2,6-dioxopyrimidine-4-carboxylic acid; H 2 sor}, was also decarboxylated in the reaction with trans-[ReOI 2 (OEt)(PPh 3 ) 2 ] in ethanol to form [Re III (cor)I(PPh 3 ) 2 ]I (2, Hcor=5-(2-hydroxybenzylideneamino)-pyrimidine-2,4(1H,3H)-dione). Decarboxylation of H 2 sor was not observed in its reaction with trans-[ReOCl 3 (PPh 3 ) 2 ], which led to the isolation of [ReOCl(sor)(PPh 3 )] (3), in which sor 2− is coordinated as a tridentate ligand as expected. Spectroscopic results and the X-ray crystal structures of compounds 1–3 are also presented.