Palladium and platinum complexes with cyclo-triphosphorus and tetrahedro-tetraphosphorus as ligands

Article abstract of DOI:10.1021/ic50225a047

Simple and triple-decker sandwich complexes of palladium and platinum containing the cyclo-triphosphorus unit as a η³ ligand with general formulas [(triphos)M(η³-P₃)]BF₄ (triphos = 1,1,1-tris((diphenylphosphino)methyl)ethane; M = Pd, Pt) and [LPd(μ-(η³-P₃))PdL]Y (L = triphos, Y = BPh₄; L = np₃, Y = BF₄; np₃ = tris(2-(diphenylphosphino)ethyl)amine) have been synthesized and characterized. The structures of the complexes [(triphos)Pd(η³-P₃)]BF₄·C ₂H₅OH (I) and [(triphos)Pd(μ-(η³-P₃))Pd(triphos)]BPh₄ (II) have been elucidated through complete X-ray analyses. The crystals of compound I are monoclinic with a = 13.084 (5) A?, b = 20.467 (7) A?, c = 17.183 (6) A?, β = 105.35 (4)°, space group P2₁/n, Z = 4, R = 0.065, and 1876 observed reflections. The crystals of the compound II are orthorhombic with a = 20.973 (7) A?, b = 18.464 (6) A?, c = 25.299 (8) A?, space group Pccn, Z = 4, R = 0.072, and 1872 observed reflections. Both in the simple and in the triple-decker sandwich complexes, the metal atom is six-coordinate. The palladium(0) compound [(np₃)Pd(η-P₄)] contains the intact tetrahedral P₄ molecule σ bonded to the metal.