The role of anions in addressing the outcome of the reaction of tetramethylthiourea with cis-Pt(II)(phos)2 moieties (phos = PPh3 or 1/2 dppe), cyclometallation vs. hydrolysis to monothiocarbamato, and the crystal structure ot trans-bis(N-dimethylmonothiocarbamato)bis(triphenylphosphane)platinum(II)

The product of the reaction between tetramethylthiourea (tmtu) and cis-PtII(phos)2 moieties (phos = PPh3, or ½ dppe) depends on the anionic species present. With NO3 –, CF3CO2 –, CF3SO3 – and BF4 –, the cyclometallate cationic complex [Pt(phos)2(tmtu*-C,S)]+ is obtained (tmtu* is tmtu deprotonated at one methyl group). The acetato and malonato complexes are inactive towards such deprotonation, but, in the presence of water, promote tmtu hydrolysis with formation of N-dimethylmonothiocarbamato (mtc) complexes in which mtc is S-coordinated. cis-[Pt(PPh3)2(mtc)2] isomerises slowly to the trans isomer, whose crystal structure is reported.