Synthesis And Transition Metal Complexes Of Bridging Acylhydrazone And Acythiourea Ligands

Acylhydrazone, acylurea and acylthiourea are a special group of Schiff bases and have stronger coordination ability and versatile complexing style. They have been used to coordinate transition metal, rear earth metal ions to form a lot of complexes and these complexes show some unusual properties which make them to be potential drugs and functional materials. The study of metal complexes of acylhydrazone, acylurea and acylthiourea has become a very hot research field of modem coordination chemistry. In this thesis we initiated the study of synthesis, multinuclear complexes and crystal structures of some phenylene bridging acylhydrazone, acylurea and acylthiourea. The main experimental results are as fellows:m-Xylene, p-xylene and 2,6-dimethylpyridine were oxidized with KMnO₄, esterified with methanol and aminolysized with hydrazine to give double acylhydrazine derivatives, which in turn reacted with salicylaldehyde and 2-pyridinecarboaldehyde to give the six m-phenylene, p-phenylene and 2,6-pyridinyl bridged double acylhydrazone ligands. These didentate ligands can form transition metal and rear earth metal complexes. As shown by X-ray crystal analysis of lead complex each lead ion show an unusually N₂O₂ distorted planar square coordination geometry. Resorcinol, isopropyl biresorcinol and m-nitrophenylresorcinarene were alkylated with ethyl chloroacetate, aminolysized with hydrazine and condensated with salicylaldehyde and 2-pyridinecarboaldehyde to give polydentate lignads with two, four, and eight acylhydrazones, which can be coordinated with transition metal ions to form multinuclear complexes. The structures of all new products were prelimarily characterized with IR, H NMR and X-ray single crystal analysis.A series of acylurea and acylthiourea have been efficiently synthesized by grinding the above mentioned acylhydrazines with butylisoyanate and phenylthioisocyanate in high yields. Their complexing reactions with transition metal ions have also conducted and the structure of the complexes needs further determination.In this thesis alkylation reactions of calix[n]arenes (n = 4, 6, 8) with 1-bromo-3-chloropropane and 1,2-dibromoethane were investigated and several new compounds have been isolated. The X-ray single crystal analysis of two representative compounds showed that the alkylation reaction of calixarene is very interesting and variable alkylated products could be produced according to reaction conditions.