Studies On Organometallic N, O-Ligands And Their Complexes

Organometallic enaminones and pyrazoles are two important ligands. They have not only various reactivities and plentiful structural chemistry but also important applications in the fields of biology, pharmacology, pesticide, catalysis and materials science.To more enrich syntheses of organometallic enaminones and explore the syntheses of acyl pyrazoles, we initiated the studies on syntheses and properties of ferrocene-containing organometallic ligands-enaminones and acyl pyrazoles and their metal complexes, making a series of significant and creative developments.The main results are as follows:Thirty new ferrocene-containing enaminones and acyl pyrazoles and their metal complexes were synthesized and fully characterized by elemental analyses, HNMR, IR and UV spectroscopies as well as by the single crystal structures of nine typical compounds determined by X-ray diffraction methods.1. Based on the research of our group, we studied the reactions of P-diketone [C₅H₅FeC₅H₄COCH₂COCH₃] (P-diketone [C₆H₅COCH₂COCH₃]) and chiral amino acid esters and chiral amines, fully studied the reactions of p-diketone [C₅H₅FeC₅H₄COCH₂COCH₃] and ethanolamines, aliphatic diamines as well as aromatic diamines, with a series of enaminone compounds synthesized. The stuctures of the products have been determined by single crystal X-ray diffraction of the typical compounds H₂L¹ HL⁴, H₂L⁵ and HL⁶.2. The reactions of P-diketone [C₅H₅FeC₅H₄COCH₂COCH₃] and alkyl dihydrazides and aryldihydrazides in the presence of p-TsOH were systematically studied. Besides the products of acyl pyrazoles, for propyldihydrazide, the product L³ is the substance which has not only the pyrazole heterocycle but the lactone heterocycle.Furthermore, the reactions of the organometallic pyrazole (the parent pyrazole, 3-ferrocenyl-5-methylpyrazole) and alkyl acyl chloride, aryl acyl chloride, aliphatic acid dichloride as well as aromatic acid dichloride were studied. The results show that the products from the reactions of P-diketone and hydrazides and the products from the reactions of the organometallic pyrazole and acyl chlorides are isomeric. The structures of compounds L¹, L₁0 (the paired isomers) and L³, L⁵ have been determined by X-ray diffraction methods.3. The coordination reactions of synthesized ligands including organometallic enaminones and organometallic pyrazoles with bivalent copper and nickel were researched in detail, with a series of compounds synthesized. The complexes synthesized were determined by elemental analyses, IR and UV spectroscopies. Besides, the crystal structure of the product L¹Cu has been determined by single crystal X-ray diffraction.