Synthesis, characterization, reactivity and computational studies of new rhenium(I) complexes with thiosemicarbazone ligands derived from 4-(methylthio)benzaldehyde

摘要: Abstract N-thioamide thiosemicarbazone derived from 4-(methylthio)benzaldehyde (R = H, HL1; R = Me, HL2 and R = Ph, HL3) have been prepared their reaction with fac-[ReX(CO)3(CH3CN)2] (X = Br, Cl) in methanol gave the adducts [ReX(CO)3(HLn)] (1a X = Cl, n = 1; 1a′ X = Br, 1b n = 2; 1b′ 1c n = 3; 1c′ n = 3) good yield. All compounds characterized by elemental analysis, mass spectrometry (ESI), IR 1H NMR spectroscopic methods. Moreover, structures of HL2, HL3, HL3·(CH3)2SO 1b′·H2O were also elucidated X-ray diffraction. In 1b′, rhenium atom is coordinated sulphur azomethine nitrogen atoms (κS,N3) forming a five-membered chelate ring, as well three carbonyl bromide ligands. The resulting coordination polyhedron can be described distorted octahedron. structure dimers based on rhenium(I) thiosemicarbazonates [Re2(L1)2(CO)6] (2a), [Re2(L2)2(CO)6] (2b) [Re2(L3)2(CO)6] (2c) determined studies. Methods synthesis optimized to obtain amounts these thiosemicarbazonate complexes. dimer are achieved Re–S–Re bridges, where S thiolate κS,N3-bidentate ligand. Some single crystals isolated 2b contain [Re(L4)(L2)(CO)3] (3b) L4 (=2-methylamine-5-(para-methylsulfanephenyl)-1,3,4-thiadiazole) originated cyclization process thiosemicarbazone. Furthermore, coordinate thioamidic (κS,N2) affording four-membered ring.