Reaction of [Pt3(μ-CO)3(PtBu3)3] with activated olefins and alkynes: the X-ray-structure of [Pt(CO)(PtBu3)(CF3Ctriple bond; length of mdashCCF3)]

The reactions of the triangulo-cluster [Pt3(μ-CO)3(PtBu3)3] with activated olefins and alkynes have been examined under various conditions. At low temperature, cluster fragmentation occurs yielding the Pt(0) complexes [Pt(CO)(PtBu3)(olefin)] (olefin = maleic anhydride and maleimide), while di(tert-butyl)acetylenedicarboxilate reacts quantitatively giving the dinuclear Pt(0) complex [Pt2(CO)2(PtBu3)2(μ–η2:η2-tBuO2CCtriple bond; length of mdashCCO2tBu)]. At higher temperature and in the presence of alkyne in large excess, the latter dimer converts quantitatively to the monomers [Pt(CO)(PtBu3)(alkyne)] (alkyne = CF3Ctriple bond; length of mdashCCF3 and tBuO2CCtriple bond; length of mdashCCO2tBu). The stereochemistry of these complexes has been established by NMR and IR measurements. The structure of [Pt(CO)(PtBu3)(CF3CCCF3)] was confirmed by X-ray diffraction analysis.