Allyl palladium dithiocarbamates and related dithiolate complexes as precursors to palladium sulfides

Allyl-palladium dithiocarbamate complexes, [Pd(allyl)(S2CNR2)], have been prepared from the addition of dithiocarbamate salts to [Pd(allyl)(μ-Cl)]2 and TGA and DSC studies have been carried out in order to assess their potential as MOCVD precursors to palladium sulfides. For comparison [(η3-C4H7)Pd(S2PPh2)] and [Pd(S2CNMeR)2] (R = Bu, Hex) have also been prepared and tested as precursors. The unsymmetrical dithiocarbamate complex, [(η3-C3H5)Pd(S2CNMeHex)], which has a melting point of 65 °C was selected as the best single source precursor and thin films of predominantly Pd2.8S were deposited on glass slides. The crystal structures of [(η3-C4H7)Pd(S2CNMe2)], [(η3-C4H7)Pd(S2CNPr2)], [(η3-C4H7)Pd(S2PPh2)] and [Pd(S2CNMeBu)2] are reported. All except [(η3-C4H7)Pd(S2CNPr2)] show weak intermolecular S⋯H or Pd⋯H interactions.