Structural investigation of homonuclear Pt-2 and heteronuclear PdPt complexes containing a metal-metal bond bridged by hydride and sulfide ligands

The complex [Pt-2(mu-H)(mu-S)(dppe)(2)](PF6) undergoes a displacive order-disorder transformation at ca 230 K. The low-temperature structure is ordered with one cation-anion pair as the asymmetric unit in space group P2(1)/n. At room temperature the b axis is halved and the space group is P2/n, imposing crystallographic twofold rotation symmetry on both ions; the anion shows major disorder and there is probably minor disorder in the cation, but its internal geometry remains essentially unchanged. The heteronuclear complex [PdPt(mu-H)(mu-S)(dppe)(2)](PF6) is isostructural with the Pt-2 complex at room temperature, All three structures have been determined crystallographically and both complexes have been extensively characterized by NMR spectroscopy, unambiguously confirming the genuine heteronuclear nature of the mixed-metal complex and the presence of the bridging hydride ligand.