The reaction of the ambidentate ligand 1,3-bis(3-methylpyridin-2-yl)thiourea ( 1) with [PtCl 2 (dmso) 2 ] in dichloromethane led to formation of a poorly soluble compound 2, characterized as a conventional chelate complex [PtCl 2 (1)] = 2. Reaction in methanol resulted in desulfurization to produce a fluorescing cationic diaminocarbeneÀ platinum(II) complex 3, the structure of which was elucidated by X-ray crystallography, mass spectrometry and NMR. Experimental findings were supported by DFT calculations.