Dithiolene-like palladium complexes of methyl 3-phenyldithio-carbazate and related derivatives. Crystal structure of [Pd{N[C6H3(OMe-4)NC6H4(OMe-4)]NC(S)SMe}(SCN)]·0.5C6H6

Abstract

The salt K₂[PdCl₄] reacted with NHRNHC(S)SMe (R = Ph, C₆H₄OMe-4 or C₆H₄NO₂-4) in strongly basic aqueous alcoholic media in the air to give deep coloured, diamagnetic, dithiolene-like complexes [Pd{NRNC(S)SMe}₂]. The ligands are N,S-chelated through the non-methylated sulfur and the terminal nitrogen. The anionic complex [AsPh₄][Pd{N(C₆H₄NO₂-4)NC(S)SMe}₂] was also isolated. Heating [Pd{NPhNC(S)SMe}₂] and [Pd{N(C₆H₄OMe-4)NC(S)SMe}₂] led to the new complexes [Pd{N(C₆H₄NPh-2) NC(S)SMe}(NCS)]·0.5C₆H₆ and [Pd{N[C₆H₃(OMe-4) NC₆H₄(OMe-4)]NC(S)-SMe}(SCN)]·0.5C₆H₆, respectively. The crystal structure of the latter was determined.