219799-85-6Relevant articles and documents
Synthesis and characterization of complexes of PdII and PtII containing the iminophosphorane ligand Ph3P=NC≡N
Falvello, Larry R.,Fernandez, Susana,Garcia, Maria M.,Navarro, Rafael,Urriolabeitia, Esteban P.
, p. 3745 - 3750 (2007/10/03)
The chemistry of the iminophosphorane Ph3P=NC≡N towards different palladium(II) and platinum(II) subtrates has been investigated. This ligand shows a high selectivity for co-ordination through the terminal N atom (that of the cyanide group), while the phosphoiminic N atom shows very poor nucleophilic ability. The reaction of [PdCl2(NCPh)2] with Ph3P=NCN (1:2 molar ratio) gives trans-[PdCl2(NCNPPh3)2] 1. The crystal structure of 1 has been determined and shows the iminophosphorane co-ordinated selectively through the nitrilic N atom. The reaction of the cationic derivatives [M(C-P)(NCMe)2][ClO4] [M = Pd or Pt; C-P = o-CH2C6H4P(C6H4Me-o) 2] with Ph3P=NCN (1:2 molar ratio) resulted in the formation of [M(C-P)(NCN=PPh3)2][ClO4] (M = Pd 2 or Pt 3), for which the same terminal N-co-ordination has been observed. The reaction of [Pd(dmba)(NCMe)2][ClO4] (dmba = C6H4CH2NMe2-2) with Ph3P=NCN (1:1 molar ratio) gave the dinuclear derivative [{Pd(μ-NCN=PPh3)-(dmba)}2][ClO4]2 4 in which the iminophosphorane acts as an N,N-bridging ligand, while reaction in 1:2 molar ratio gave [Pd(dmba)(NCN=PPh3)2][ClO4] 5 which possess N-terminal co-ordination. The reaction of this iminophosphorane with monosolvate complexes [Pd(dmba)(PPh3)(THF)][ClO4] or [Pt(C-P)(PPh3)(NCMe)][ClO4] (1:1 molar ratio) resulted in the formation of [Pd(dmba)(PPh3)(NCN=PPh3)][ClO4] 6 or [Pt(C-P)(PPh3)-(NCN=PPh3)][ClO4] 7, and the reaction with the halide bridging derivatives [{Pd(μ-Cl)(dmba)}2] or [{Pt(μ-Cl)-(C-P)}2] (2:1 molar ratio) produced cleavage of the bridging system and formation of [PdCl(dmba)(NCN=PPh3)] 8 and [PtCl(C-P)(NCN=PPh3)] 9. The same N-terminal co-ordination mode is observed in complexes 6-9.
