Crystal and molecular structure of µ-sulphido-carbonyltris(triphenylphosphine)diplatinum(II): a complex with a platinum–platinum covalent bond

Abstract

The crystal and molecular structure of µ-sulphido-carbonyltris(triphenylphosphine)diplatinum(II) has been determined from three-dimensional X-ray diffractometer data. The crystals are triclinic with Z= 2 in a unit cell of dimensions a= 10·687, b= 25·240, c= 9·307 Å, α= 95·17, β= 104·22, and γ= 97·67°. The structure was refined by least-squares methods using 2897 independent reflections to R 0·069. The molecules conform essentially to the P space group, although there is disorder in the carbonyl and one of the triphenylphosphine groups to give two conformational isomers. The complex contains a single covalent Pt–Pt bond which forms with sulphur a three-membered ring. The Pt–Pt bond distance is 2·647 (σ 0·002)Å, and the Pt–S distances are 2·218 (σ 0·009) and 2·227 (σ 0·009)Å. The Pt–S–Pt angle is 73·1° and the mean Pt–Pt–S angle is 53·5°. The platinum atoms and their immediate neighbours are essentially planar, although the co-ordination about the metal atoms is far from square-planar.