The complex cis-[PtCl₂(Me₂SO)₂] (1) reacts with 1 equiv. of C-4-trifluoromethylphenyl-N-methylaminonitrone (2) to give the product [PtCl(Me₂SO){ON(Me)C(4-CF₃C₆H₄)NH}] (3; 75%). Treatment of 3 with an excess cyclohexyl isocyanide, CyNC, leads to the acyclic diaminocarbene complex [PtCl(CNCy){N(Me)C(4-CF₃C₆H₄)NC(=NHCy)}] (4; 28%). The latter exhibits solid-state phosphorescence with an emission maximum at 600 nm and 23% quantum yield. Complexes 3 and 4 were characterized by HRESI⁺-MS, FTIR, ¹H and ¹³C{¹H} NMR spectroscopic techniques. The complex 4 was additionally characterized by X-ray diffraction; short Pt[pdbond]Pt contacts (3.2360(5) Å) were observed in the crystal structure. These non-covalent interactions have an attractive nature and their estimated strength is 4.6–5.6 kcal/mol.