Synthesis and characterisation of cyanodithioimidocarbonate [C2N2S2]2− complexes

Abstract

[PPh₄]₂[M(C₂N₂S₂)₂] (M = Pt, Pd) and [Pt(C₂N₂S₂)(PR₃)₂] (PR₃ = PMe₂Ph, PPh₃) and [Pt(C₂N₂S₂)(PP)] (PP = dppe, dppm, dppf) were all obtained by the reaction of the appropriate metal halide containing complex with potassium cyanodithioimidocarbonate. The dimeric cyanodithioimidocarbonate complexes [{Pt(C₂N₂S₂)(PR₃)}₂] (PR₃ = PMe₂Ph), [M{(C₂N₂S₂)(η⁵-C₅Me₅)}₂] (M = Rh, Ir)and [{Ru(C₂N₂S₂)(η⁶-p-MeC₆H₄ⁱPr)}₂] have been synthesised from the appropriate transition metal dimer starting material. The cyanodithioimidocarbonate ligand is S,S and bidentate in the monomeric complexes with the terminal CN group being approximately coplanar with the CS₂ group and trigonal at nitrogen thus reducing the planar symmetry of the ligand. In the dimeric compound one of the sulfur atoms bridges two metal atoms with the core exhibiting a cubane-like geometry.