Letter | Published:

Binding of the Thiocyanate Ion in Complexes with Palladium (II)-containing Tertiary Phosphines

Naturevolume 199pages803804 (1963) | Download Citation



THE infra-red spectra of several thiocyanate complexes of platinum and palladium suggest that these metals must be bound to nitrogen in compounds with the general formula [M(PR3)2(CNS)2] (R = aliphatic tertiary phosphine)1. Adams and Booth more recently reported that platinum must be co-ordinated to nitrogen in the complexes trans-[Pt(CNS)CH3(PEt3)2] and trans-[Pt(CNS) (COCH3)(PEt3)2] (ref. 2). On the other hand, palladium and platinum invariably appear to be bound through sulphur in a variety of complexes with the thiocyanate ion and other different ligands3. It thus appears that the binding of these metal ions with the thiocyanate group is peculiarly affected by the presence of phosphine ligands in the molecule of the complex. The occurrence of this unexpected nitrogen-metal binding may be of more general interest, being clearly related to important changes in the binding properties of the metal ions brought about by the presence of the phosphine ligands. However, all the previous evidence on which these conclusions were based came exclusively from infra-red spectra. A more direct demonstration of the nature of the metal-thiocyanate bond seemed desirable to us. Therefore, a determination by X-ray analysis of the structure of the compound [Pd(PPr3n)2(CNS)2] was undertaken to resolve the question of the bonding of the thiocyanate group.

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  1. 1

    Turco, A., and Pecile, C., Nature, 191, 66 (1961).

  2. 2

    Adans, % %, and Booth, % %, J. Chem. Soc., 1112 (1962).

  3. 3

    Giacometti,, Pecile, C., and Turco, A., Abst. Seventh Conf. Coordination Chemistry, 9 (Stockholm, 1962).

  4. 4

    Owston, %, and Rowe, % %, Acta Cryst., 13, 253 (1960).

  5. 5

    Cotton, % %, Goodgame, % %, and Sacco, % %, J. Amer. Chem. Soc., 83, 4157 (1961).

  6. 6

    Pecile, C., and Turco, A. (unpublished results).

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  1. Centro Strutturistica Chimica CNR, Istituto Chimica Generale, University of Padova, Italy

    • E. FRASSON
    • , C. PANATTONI
    •  & A. TURCO


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