Syntheses of New Sulfur−Nitrogen Palladacycles − Crystal Structures of [(AMTTO)PdBr2]2·3.5THF, [(AMTTO)PdI2]2·3MeOH, [(AMTTO)Pd(PPh3)Br]Br·MeOH, and [(AMTTO)Pd(PPh3)I]·2MeOH (AMTTO = 4-Amino-6-methyl-1,2,4-triazine-3-thione-5-one)

Reactions of [(AMTTO)PdCl2]·MeOH (1) with sodium bromide and sodium iodide led to the palladacycles [(AMTTO)PdBr2]2·3.5THF (2) and [(AMTTO)PdI2]2·3MeOH (3) in excellent yields. Treatment of 2 and 3 with triphenylphosphane gave the complexes [(AMTTO)Pd(PPh3)Br]Br·MeOH (4) and [(AMTTO)Pd(PPh3)I]·2MeOH (5), respectively. All the complexes have been characterized by IR spectroscopy, elemental analysis, as well as by X-ray diffraction studies. In addition, 4 and 5 have been characterized by 31P NMR spectroscopy. Crystal data for 2 at −80 °C: triclinic, space group P1¯, a = 1150.8(1), b = 1234.1(1), c = 1398.1(1) pm, α = 84.01(1)°, β = 86.84(1)°, γ = 66.40(1)°, Z = 2, R1 = 0.0366; for 3 at −50 °C: orthorhombic, space group Pbcn, a = 1476.2(1), b = 1333.1(1), c = 1440.1(1) pm, Z = 4, R1 = 0.0302; for 4 at −80 °C: monoclinic, space group P21/c, a = 993.0(1), b = 993.6(1), c = 2735.5(2) pm, β = 97.64(1)°, Z = 4, R1 = 0.0464; for 5 at −70 °C: monoclinic, space group P21/c, a = 865.7(2), b = 3760.5(3), c = 861.1(1) pm, β = 97.56(1)°, Z = 4, R1 = 0.0613.