الفهرس | Only 14 pages are availabe for public view |
Abstract The overall aim of thesis is to study the preparation and characterization of new ruthenium(II)/(III) complexes with dicarboxylate ligands. Also, studying the preparation and characterization of new copper(II) complexes with 2,3dihydroxybenzaldehyde N(4) substituted thiosemicarbazone ligands. The application of some of these complexes towards catalytic oxidation of primary and secondary alcohols into the corresponding aldehydes or ketones and also oxidation of 3,5ditert butylcatechol (DTBCat) into 3,5ditertbutylquinone are of particular interest. 1. The first part deals with ruthenium(II)/(III) complexes with dicarboxylate ligands. The uses of these complexes as catalytic oxidants for the oxidation of primary alcohols to aldehydes and secondary alcohols to ketones are studied in the presence of tBuOOH or NMO as cooxidants. A number of ruthenium(II)/(III) complexes of the type [RuII(bpy)2L?].4H2O; [Ru2III(bpy)4L??2]; [RuII(PPh3)3L?(H2O)] and [Ru2(PPh3)6L??2(H2O)2] (L? = dianions of oxalate or malonate; L?? = dianions of phthalate or succinate) have been isolated, characterized by spectroscopic techniques and investigated by cyclic voltammetry. These ruthenium complexes were found to be effective catalysts towards oxidation of alcohols into the corresponding aldehydes or ketones, which attributed to the dimeric nature of these complexes, are due to the reversible reduction of RuIII RuIII into RuII RuII and oxidation of RuII RuII to RuIII RuIII. 2. The second part of this work is concerned with preparation and characterization of copper(II) complexes of the type [CuII(H2L)(NO3)(H2O)] and [CuII(HL3)(H2O)], (H2L = H2L1, H2L2 ; H3L or H3L3 = 2,3dihydroxybenzaldehyde N(4)substituted thiosemicarbazones) . Their properties as catalytic oxidants have also been studied. These complexes are effective catalysts for oxidation of 3,5ditertbutylcatechol into the corresponding 3,5ditertbutylquinone in the presence of O2 or tBuOOH as cooxidants. |