New thiocarbamate and thioureate palladium and platinum complexes: synthesis and use as metalloligands. Unprecedented coordination of the thioureate ligand in [(C6F5)2Pd{μ2,η2-SC(NMe2)NPh}Pd(C6F5)(bpzm)]

The di-μ-hydroxo complexes [NBu4]2[{(C6F5)2M(μ-OH)}2] (M=Pd, Pt) react with PhNCS in alcohol ROH solution to yield the N,S-chelating thiocarbamate metal complexes [NBu4][(C6F5)2M{η2-SC(OR)NPh}] (R=Me, Et or Prn). [NBu4]2[{(C6F5)2Pd(μ-OH)}2] also reacts with PhNCS in the presence of dialkylamines R2NH to yield the N,S-chelating thioureate (1−) palladium complexes [NBu4][(C6F5)2Pd{η2-SC(NR2)NPh}] (R=Me or Et). [NBu4][(C6F5)2M{η2-SC(X)NPh}] (M=Pd or Pt; X=OMe or NR2) reacts with [(C6F5)Pd(bpzm)(acetone)]ClO4 to yield the dinuclear complexes [(C6F5)2M{(μ2,η2-{SC(X)NPh}Pd(C6F5)(bpzm)] (M=Pd or Pt, X=OMe or NR2; bpzm=bis(3,5-dimethylpyrazol-1-yl)methane). The single-crystal structures of [NBu4][(C6F5)2Pd{η2-SC(OMe)NPh}] and [(C6F5)2Pd{μ2,η2-SC(NMe2)NPh}Pd(C6F5)(bpzm)] have been established by X-ray diffraction.