Abstract
The mixed ligand complexes PtX 2(ER 3)L and PtXY(ER 3)L (where ER 3 = PR 3 or AsMe 3; L = phosphine, arsine; X = Cl; Y = Cl, H or Me) have been prepared and characterized. Reaction of PtMe 2(ER 3)L with HCl yields PtMeCl(ER 3)L, in exclusively one of three possible isomeric forms. Excess tetramethyltin reacts with Pt 2Cl 2(μ-Cl) 2(PMe 2Ph) 2 giving both cis and trans Pt 2(μ-Cl) 2(PMe 2Ph) 2, as identified from the NMR spectra. Cleavage of Pt 2(μ-Cl) 2Me 2(PMe 2Ph) 2 with donor ligands such as AsPh 3, PMe 2 or pyridine, was useful as a synthetic route to the unsymmetrical methylchloro Pt II derivatives. The reaction of cis-[PtMe 2(PPh 3)(AsPh 3)] with excess dimethylacetylenedicarboxylate (DMA) yielded only one product, which was of the formula trans-[Pt{C(COOCH 3)C(COOCH 3)CH 3} 2(PPh 3)(AsPh 3)], with the alkenyl groups having the same geometry about the CC bond. The use of diethylacetylene-dicarboxylate (DEA) rather than DMA gave a similar product. However, when cis-[PtMe 2(PEt 3)(AsPh 3)] was allowed to react with DMA, two products of the formula trans-[Pt{C(COOCH 3)C(COOCH 3)CH 3} 2(PEt 3)(AsPh 3)] were obtained, with the stereochemistry of both alkenyl groups being either cis or trans.
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