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.