Synthesis and characterisation of cyanodithioimidocarbonate [C₂N₂S₂]^2- complexes

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)(eta(5)-C5Me5)}(2)] ( M = Rh, Ir) and [{Ru(C2N2S2)(eta(6)-p-(MeC6H4Pr)-Pr-i)}(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.