The reaction of cis-[PtCl2(PPh3)2] with trisubstituted thioureas [R1R2NC(=S)NHR3] in refluxing methanol with triethylamine base, followed by addition of NaBPh4 gives the salts [Pt{SC(=NR1R2)NR3}(PPh3)2]BPh4 in high yield; a range of thiourea substituents, including chiral, fluorescent and chromophoric groups can be incorporated. The azo dye-derived complex [Pt{SC(=N(CH2CH2)2O)NC6H4N=NC6H4NMe2}(PPh3)2]BPh4 has been characterised by a single-crystal X-ray diffraction study. The formation of a fluorescein-derivatised platinum-thiourea complex is also described. Reaction of cis-[PtCl2(PPh3)2] with PhNHC(S)NHPh or EtNHC(S)NHEt, triethylamine and NaBPh4 gives, respectively, [Pt{SC(=NHPh)NPh}(PPh3)2]+ and the known cation [Pt{SC(=NHEt)NEt}(PPh3)2]+, isolated as tetraphenylborate salts. Reaction of cis-[PtCl2(PPh3)2] with an excess of Na[MeNHC(S)NCN] in methanol gives the bis(thiourea monoanion) complex trans-[Pt{SC(=N---CN)NHMe}2(PPh3)2], characterised by NMR spectroscopy and an X-ray crystal structure determination. When cis-[PtCl2(PPh3)2] is reacted with 1 equiv. of Na[MeNHC(S)N---CN] in methanol, with added NaBPh4, a mixture of isomers of the [Pt{SC(=NHCN)NMe}(PPh3)2]+ cation is obtained.
