Synthesis and structures of palladium(II) and platinum(II) complexes containing heterocyclic thiolate ligands formed by cycloaddition reactions of coordinated azides

The phosphine-stabilized azido complexes [M(N-3)(2)(PTA)(2)] (M = Pd, Pt; PTA = 1,3,5-triaza-7-phosphaadamantane) were prepared in high yields by a ligand exchange reaction from cis-[Pd(N-3)(2)(tmeda)] and cis-[Pt(N-3)(2)(cod)], respectively. The Pd and Pt complexes [M(N-3)(2)(PTA)(2)] undergo cycloaddition reactions with various isothiocyanates to give complexes containing anionic, S-coordinated tetrazole-thiolate ligands of the type trans-[M(SCN4R)(2)(PTA)(2)] (M = Pd, Pt; R = Et, allyl, Me, Ph). The molecular structures of several of these derivatives were determined by X-ray crystallography.