Phosphino-amino-thiazolines and -thiazoles can exist in solution in two tautomeric forms, in which the N-H proton involves the endo-cyclic or exo-cyclic nitrogen atom. The two tautomers show different reactivities toward alcoholysis; the imino form degrades more rapidly. Their bischelated platinum complexes were studied in the solid state by single crystal X-ray diffraction. Thus, the unique stereoelectronic features of the [Pt(PN(th))] (PN(th)=diphenylposphino-aminothiazoline) moiety were revealed. The complex cis-[Pt(PN(th))(2)] reacts with gold(I) salts to yield dimetallic compounds, the molecular structures of which have been determined by X-ray diffraction. Solid cis-[Pt(PN(th))(2)] shows vapoluminescent properties if exposed to alcohol vapors. A combined photophysical and crystallographic investigation has been carried out to clarify the unprecedented rigidochromic role of the alcohol in this phenomenon.
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