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DOI: 10.1039/A904859F (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 3877-3882

Platinum assisted cyclization of S-methyl 3-acyl-2-methyldithiocarbazates under mild conditions. Crystal structure of [Pt2(µ-SMe)(terpy)2][ClO4]3[hair space]†

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Giuliano Annibale, Paola Bergamini, Valerio Bertolasi, Michela Cattabriga, Antonio Lazzaro, Andrea Marchi and Gianni Vertuani

Abstract

The reaction of the newly synthesized aqua complex [Pt(terpy)(OH2)][BF4]2 with S-methyl 3-acyl-2-methyldithiocarbazates under a variety of experimental conditions has been studied. Using a 2∶1 metal to ligand ratio in methanol, a platinum assisted cyclization was observed. The reaction products were Δ2-1,3,4-oxadiazoline-5-thione derivatives and the binuclear tricationic complex [Pt2(µ-SMe)(terpy)2]3+ whose molecular structure has been determined by X-ray crystallography. This platinum assisted transformation is proposed as a new synthetic route to Δ2-1,3,4-oxadiazoline-5-thiones under mild conditions. In the presence of an excess of a non-co-ordinating acid (HClO4, CH3SO3H or CF3SO3H) the cyclization is completely quenched and complexes with co-ordinated S-methyl 3-acyl-2-methyldithiocarbazates have been isolated. A general mechanism which accounts for the observed transformations is proposed on the basis of 1H NMR and UV/Vis evidence.

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