Cationic palladium and platinum complexes with diolefin ligands

Abstract

Chlorine-bridged complexes [M2(diolefin)2Cl2][BF4]2 have been prepared from [M(diolefin) Cl2][M = Pd or Pt; diolefin = cyclo-octa-1,5-diene (cod) or norborna-2,5-diene (nbd)] and [Et3O][BF4]. The complex [Pd(cod)2Cl2][BF4]2 rapidly forms 5,6-η-cyclo-oct-5-enyl complexes [Pd2(2-Rcot)2Cl2](R = MeO, MeCO2, or HO) with MeOH, MeCO2H, or H2O; PPh3 displaces the cod to form [Pd2Cl2(PPh3)4][BF4]2, but the plantinum analogue forms [Pt(cod)Cl(PPh3)][BF4]. Complexes [M(diolefin)Cl(PR3)]X (X = SFO3, BF4, or ClO4) have been obtained from sym,trans-[M2Cl4(PR3)2] and the diolefin with SFO2(OMe)–C6H6, [Et3O][BF4]–CH2Cl2, or Na[ClO4]–Me2CO.