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DOI: 10.1039/A805147J (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 3745-3750

Synthesis and characterization of complexes of PdII and PtII containing the iminophosphorane ligand Ph3P[double bond, length half m-dash]NC[triple bond, length half m-dash]N

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Larry R. Falvello, Susana Fernández, María M. García, Rafael Navarro and Esteban P. Urriolabeitia

Abstract

The chemistry of the iminophosphorane Ph3P[double bond, length half m-dash]NC[triple bond, length half m-dash]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[double bond, length half m-dash]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[double bond, length half m-dash]NCN (1∶2 molar ratio) resulted in the formation of [M(C–P)(NCN[double bond, length half m-dash]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[double bond, length half m-dash]NCN (1∶1 molar ratio) gave the dinuclear derivative [{Pd(µ-NCN[double bond, length half m-dash]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[double bond, length half m-dash]PPh3)2][ClO4] 5 which possess N-terminal co-ordination. The reaction of this iminophosphorane with monosolvate complexes [Pd(dmba)(PPh3)(THF[hair space])][ClO4] or [Pt(C–P)(PPh3)(NCMe)][ClO4] (1∶1 molar ratio) resulted in the formation of [Pd(dmba)(PPh3)(NCN[double bond, length half m-dash]PPh3)][ClO4] 6 or [Pt(C–P)(PPh3)(NCN[double bond, length half m-dash]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[double bond, length half m-dash]PPh3)] 8 and [PtCl(C–P)(NCN[double bond, length half m-dash]PPh3)] 9. The same N-terminal co-ordination mode is observed in complexes 6–9.

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