The complex [Pt(cod)Cl2](cod = cycloocta-1,5-diene, C8H12) reacted with 2 equivalents of PPh3 and an excess of 5-aminoorotic acid (5-amino-2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylic acid, H4L) in the presence of silver(I) oxide to give two isomers of [Pt(PPh3)2(H2L)]1 and 2. Complexes 1 and 2 can be separated by fractional crystallisation but, in CDCl3 solution, each slowly converts into an equilibrium mixture of the two. Crystal structure determinations have shown that in both 1 and 2 the 5-aminoorotate ligand co-ordinates to the platinum atom as a dianion. In 1 this is achieved via deprotonation of the carboxylic acid and the loss of an amino NH2 proton, leading to a six-membered chelate ring, whereas in 2 it is by deprotonation of the carboxylic acid and loss of the amido proton, leading to a five-membered chelate ring. This difference in co-ordination mode leads to a difference in the orientation of the hydrogen-bond donors and acceptors remaining on the ligand which, in turn, leads to different supramolecular structures, dimers for 1 and tetramers for 2, with the latter structurally similar to guanine tetrads. These naturally occurring units are stabilised by alkali-metal ions, but reaction of 2 with a compound such as NaBF4 in a two-phase dichloromethane–water system led to [Pt2(PPh3)4(HL)][BF4] as the only platinum-containing product. A crystal structure determination showed that in this complex the ligand is trianionic, deprotonated at the carboxylic acid and both the amido and amino nitrogen atoms, co-ordinating to two platinum atoms via five- and six-membered chelate rings. When dppe [1,2-bis(diphenylphosphino)ethane] was used instead of PPh3 only one isomer of [M(dppe)(H2L)](M = Pt 3 or Pd 4) was observed for both platinum and palladium, containing the five-membered chelate ring.