The reaction of Xa2[PdCl4] with diphenyl disulfide in methanol yields a polymeric compound of formula [Pd(SC6H5)Cl]n (I) containing alternating halogen and sulfur bridges. This compound is also formed by refluxing [Pd((C6H5)2S2)Cl2]2 in methanol. The characterization of I was based on its infrared spectra and on its bridge-splitting reactions. In the reaction of I with a neutral ligandL (L = pyridine, triphenylphosphine, triphenylarsine)S-bridged complexes of the type [Pd(SC6H5)-LCl]2 are formed. The reaction with ethylenediamine yields the cationic S-bridged complex [Pd(SC6H5)(en)]2Cl2, whereas with [As(C6H5)4]Cl the cationic complex [Pd(SC6H5)Cl2]2[As(C6H5)4]2 is formed. The above reactions involve only splitting of the bridges. When I reacts either with 1,2-bis(diphenylphosphino)ethane or with an excess of phosphine, both the halogen and sulfur bridges are cleaved. The nature of the products in the bridge-splitting reactions has been determined on the basis of elemental analysis, ir spectra, conductivity, and molecular weight measurements, where possible. © 1970, American Chemical Society. All rights reserved.
Polynuclear Complexes of Palladium(II) with Halogen and Sulfur Bridges
TONIOLO, Luigi;
1970-01-01
Abstract
The reaction of Xa2[PdCl4] with diphenyl disulfide in methanol yields a polymeric compound of formula [Pd(SC6H5)Cl]n (I) containing alternating halogen and sulfur bridges. This compound is also formed by refluxing [Pd((C6H5)2S2)Cl2]2 in methanol. The characterization of I was based on its infrared spectra and on its bridge-splitting reactions. In the reaction of I with a neutral ligandL (L = pyridine, triphenylphosphine, triphenylarsine)S-bridged complexes of the type [Pd(SC6H5)-LCl]2 are formed. The reaction with ethylenediamine yields the cationic S-bridged complex [Pd(SC6H5)(en)]2Cl2, whereas with [As(C6H5)4]Cl the cationic complex [Pd(SC6H5)Cl2]2[As(C6H5)4]2 is formed. The above reactions involve only splitting of the bridges. When I reacts either with 1,2-bis(diphenylphosphino)ethane or with an excess of phosphine, both the halogen and sulfur bridges are cleaved. The nature of the products in the bridge-splitting reactions has been determined on the basis of elemental analysis, ir spectra, conductivity, and molecular weight measurements, where possible. © 1970, American Chemical Society. All rights reserved.
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