Synthesis, Characterization and Crystal Structures of new Palladium(II) Complexes and the first Platinum(III) Complex Containing ATT (ATT = 6‐Aza‐2‐thiothymine)

Treatment of the ligand 6‐aza‐2‐thiothymine (ATT, HL, 1 ) with palladium chloride in methanol forms the ionic complex [(HL) 4 Pd]Cl 2 ·8MeOH ( 2 ), while its reaction with palladium iodide in same solvent produces the neutral complex trans ‐[(HL) 2 PdI 2 ]·2MeOH ( 3 ) in high yields. The reaction of 1 with Na 2 [PdCl 4 ] in the presence of sodium acetate in a molar ratio of 2:1:2 and with platinum(II) chloride in presence of sodium acetate led to the dimer tetranuclear complexes [(L 4 Pd 2 )NaCl] 2 ·8MeOH ( 4 ) and [L 4 Pt 2 Cl 2 ]·6MeOH·H 2 O ( 5 ). The latter is the first Pt III complex of the ligand. All complexes were characterized by elemental analyses and IR spectroscopy and the crystal structures of 2 , 3 , 4 and 5 are determined by single‐crystal X‐ray diffraction. Crystal data for 2 at −80 °C: triclinic space group ${\rm P}{\bar 1}$ , a = 1006.6(1), b = 1006.9(1), c = 1158.1(1) pm, α = 85.20(1)°, β = 83.84(1)°, γ = 88.91(1)°, Z = 1, R 1 = 0.0278; for 3 at −80 °C: triclinic space group ${\rm P}{\bar 1}$ , a = 490.5(1), b = 977.2(2), c = 1116.8(2) pm, α = 90.26(1)°, β = 102.33(1)°, γ = 96.08(1)°, Z = 1, R 1 = 0.0394; for 4 at −80 °C: orthorhombic space group Ccca, a = 1791.7(2), b = 1874.1(2), c = 2044.0(1) pm, Z = 4, R 1 = 0.0341 and for 5 at −80 °C: monoclinic space group P2 1 /c, a = 1464.3(1), b = 2003.7(1), c = 1368.5(1) pm, β = 95.66(1)°, Z = 4, R 1 = 0.0429.