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Synthesis and characterization of ruthenium and osmium complexes of heterocyclic bidentate ligands (N, X), X = S, Se
Authors:Antonio Sousa-Pedrares  Jaime Romero  Juan C Monteagudo  Jonathan R Dilworth
Institution:a Departamento de Química inorgánica, Universidad de Santiago de Compostela, 15782 Santiago de Compostela, Spain
b Departamento de Química Física, Universidad de Santiago de Compostela, 15782 Santiago de Compostela, Spain
c Inorganic Chemistry Laboratory, University of Oxford, Oxford OXI 3QR, UK
Abstract:The reaction of RuCl2(PPh3)3] and OsBr2(PPh3)3] precursors with a series of heterocyclic bidentate (N, X) ligands, X = S, Se, gave complexes M(R-pyS)2(PPh3)2], (R = H, 3-CF3, 5-CF3, 3-Me3Si); M(R-pymS)2(PPh3)2], (R = 4-CF3, 4,6-MeCF3) and M(R-pySe)2(PPh3)2], (R = H, 3-CF3, 5-CF3), where M is Ru or Os, pyS and pymS the anions of pyridine-2-thione and pyrimidine-2-thione, respectively, and pySe is the anion produced by the reductive cleavage of the Se-Se bond in the dipyridyl-2,2′-diselenide. All of the compounds obtained were characterized by microanalysis, IR, FAB, NMR spectroscopy and by cyclic voltammetry. Compounds Ru(3-CF3-pyS)2(PPh3)2] · 2(CH2Cl2) (2), Ru(3-Me3Si-pyS)2(PPh3)2] (4), Ru(4-CF3-pymS)2(PPh3)2] (5), Ru(3-CF3-pySe)2(PPh3)2] · 2(CH2Cl2) (8), Os(3-CF3-pyS)2(PPh3)2] · (CHCl3) (11), Os(3-Me3Si-pyS)2(PPh3)2] (13), Os(3-CF3-pySe)2(PPh3)2] · 2(CH2Cl2) (17), Os(5-CF3-pySe)2(PPh3)2] · 2(H2O) (18) and OsCl2(4,6-MeCF3-pymS)(PPh3)2] (19) were also characterized by X-ray diffraction. In all cases, the metal is in a distorted octahedral environment with the heterocyclic ligand acting as a bidentate (N, S) chelate system.
Keywords:Ruthenium complexes  Osmium complexes  Heterocyclic thiones  Selenolates
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