Synthesis And Application Of N, O-Bidentate Metal Complexes

In recent years, organometallic chemistry, as a frontier discipline, has rapidly developed. It brokes the boundary between inorganic chemistry and organic chemistry, and has remarkable achievements in theoretical research and application. It is closely interrelated with petrochemical industry, pharmacy and materials science. Zinc is a constituent and activator of over 150 different enzymes of metabolic pathways; e.g., it is present in the active site in hydrolytic enzymes, and it is a constituent of the hormone insulin. The importance of zinc in bioinorganic chemistry and organic chemistry and has prompted people to extend studies on the synthesis and solid-state structures of chelated N, O to zinc derivatives.Our research group has a long fascination on the structure and catalytic applications of N, O-bidentate metal complexes. In this essay, a series of compounds of aluminum and zinc were designed and synthesized, the main contents are divided into four chapters:Chapter 1. The research background of this thesis, including four parts: (1) research progress of N, O-bidentate ligand and their metal complexes; (2) research progress of Tishchenko reaction; (3) research progress of amidation.Chapter 2. A series of N, O-bidentate ligands were prepared from N,N-Dimethyl aniline and N,N-dimethyl-o-toluidine, as well as different aldehydes and ketones. Their organometallic complexes were synthesized by the reaction of ligand with AlMe3 or ZnEt2. All the complexes were characterized by NMR and X-ray diffraction analyses.Chapter 3. Organometallic complexes synthesized in Chapter 2 were used to catalyze the Tishchenko reaction of aldehyde. The optimal conditions were investigated.Chapter 4. Several amidinolithiums on the catalytic effect of amidation were investigated, Li[(C6H6)NHCHN(C6H6)] exhibits the highest catalytic activity. Under 25℃, the reaction of aniline with benzaldehyde catalyzed by Li[(C6H6)NHCHN(C6H6)] (10 mol%) could proceed smoothly in Et2O (10mL). The highest yield is up to 87.8%.