80% |
In methanol at 50 - 60℃; |
2.2 Synthesis of Pd(II) complexes (1-8)
General procedure: A solution of N,N,N'-trisubstitutedacyl thiourea (0.564mmol) and phosphine ligand (0.564mmol) in a minimal amount of methanol, was added drop wise to a solution of K2PdCl4 (0.564mmol) in 40mL of methanol at 50-60°C. The resulting mixture was stirred for 3-4 h and the precipitated complexes (1-8) (Scheme 1 ) were filtered, and washed with methanol. Single crystal X-ray diffraction measurement quality crystals were obtained by slow evaporation of chloroform/methanol (3:1) solution of the complexes. The 1H and 13C NMR, FT-IR, the elemental analyses, melting point data for the complexes (1-8) are as follows:(5) (Tri(m-tolyl)phosphine-κP)(1-(3-fluorobenzoyl)-3-(N-methylphenyl)thioureido-κ2(O, S)palladium(II) chloride Quantities used were 0.184 g (0.564 mmol) K2PdCl4, 0.163 g (0.564 mmol) 1-(3-fluorobenzoyl)-3-(N-methylphenyl)thiourea, 0.172 g (0.564 mmol) tri(m-tolyl)phosphine in methanol. Yield ≥ 80%; Orange solid; m.p. 206-208 °C. FTIR (cm-1) 3148(w), 3004(w), 2881(w), 2837(w), 1614(m), 1592(m), 1512(s), 1428(s), 1368(w), 1313(w), 1249(w), 1188(w), 1095(w), 1070(w), 1023(w), 999(w), 948(s), 914(s), 861(s), 781(s), 749(s), 690(s), 617(w); 1H NMR (300 MHz, CDCl3) δ 2.29 [(s, 9H, 3(-CH3)], 3.60 (s, 3H, N-CH3), 7.07-8.20 (m, 21H, ArH); 13C NMR (75.5 MHz, CDCl3) δ 21.3 (3C), 42.3 (1C), 116.7 & 117.0 (1C, d, 13C-19F, 2J = 22.7 Hz), 118.6 & 118.9 (1C, d, 13C-19F, 2J = 21.1 Hz), 126.1 (C), 126.2 (C), 127.6 (C), 127.7(3C), 127.9 (3C), 128.1(C), 128.3 (3C), 129.4 (3C), 132.0 (3C), 135.3(1C), 135.4 & 139.0 (1C, d, 13C-19F, 1J = 276 Hz), 137.8 (C), 145.4 (C), 165.2(C), 171.2 (1C, C=O), 174.6 (1C, C=S); 31P NMR (121.5 MHz, CDCl3) δ 34.84; Anal. Calc. for C36H33ClFN2OPPdS (Mol. mass: 733.57) C, 58.94; H, 4.53; N, 3.82; S, 4.37. Found: C, 58.83; H, 4.48; N, 3.85; S, 4.32. |