Different co-ordination modes of the ligand [SPPh2]– in complexes of PdII and PtII. Crystal structures of [{Pd(µ-SPPh2)(C6F5)(PPh3)}2] and [Pd(SPPh2)(PPh3)2]ClO4·CH2Cl2

Abstract

The neutral complexes [{M(µ-SPPh₂)(C₆F₅)(PR₃)}₂](M = Pd or Pt; PR₃= PPh₃ or PPh₂Et) containing the P,S-bridging [SPPh₂]^– have been synthesised by reaction of the corresponding acetylacetonate (acac) derivatives [M(C₆F₅)(acac-O,O′)(PR₃)] with HP(S)Ph₂. However, the reaction of the cationic complexes [M(acac-O,O′)(PPh₃)₂]ClO₄(M = Pd or Pt) with HP(S)Ph₂ affords mononuclear [M(SPPh₂)(PPh₃)₂]ClO₄ in which the [SPPh₂]^– ligand is co-ordinated as a P,S-chelate. The anionic complex [NBu₄]₂[{Pd(µ-SPPh₂)(C₆F₅)₂}₂] has also been synthesised. The crystal structures of [{Pd(µ-SPPh₂)(C₆F₅)(PPh₃)}₂] and [Pd(SPPh₂)(PPh₃)₂]ClO₄·CH₂Cl₂ have been determined by X-ray diffraction methods; the former adopts a boat conformation.