Acta Crystallographica Section B

Structural Science

Volume 52, Part 2 (April 1996)

research papers

Acta Cryst. (1996). B52, 270-276 [ doi:10.1107/S0108768195010640 ]

Structural investigation of homonuclear Pt₂ and heteronuclear PdPt complexes containing a metal-metal bond bridged by hydrido and sulfido ligands

W. Clegg, M. Capdevila, P. González-Duarte and J. Sola

Abstract: The complex [Pt₂(-H)(-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 P2₁/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(-H)(-S)(dppe)₂](PF₆) is isostructural with the Pt₂ 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.