Synthesis And Catalysis Of Amidino-metal Complexes

Organometallic chemistry is one of the cornerstones of organic synthesis. It is closely interrelated with catalysis, materials science, life science. The modern development of organometallic chemistry has also seen amidinates come to the fore as support ligands in homogeneous catalysis. In doing so, amidinates have availed themselves well amongst organocarbides due to their flexibility, which offers a bounty of coordination modes, and ease of synthesis, placing them very much at the fore of the organometallic chemistry.Our reseach group has a long fascination with the structure and catalytic applications in organometallic amidinate chemistry. This essay is developed on the basis of the above ideology. Details are elaborated as following:Chapter1. The research background of this thesis, including three parts:(1) research progress of amidino-lithium/aluminium/zinc complexes;(2) research survey and synthetic method of inverse crown ether complexes;(3) research progress of Tishchenko reaction.Chapter2. Focus on the oxophilicity of amidinolithium complexes. Several inverse corwn ether complexes contain O2-/O2-2were synthesized by reaction of amidinolithium with O2/H2O and characterized by NMR and X-ray single crystal diffraction analysis. Isolation and structural characterization of the resulting complexes have afforded us some understanding of the processes active during oxygen scavenging.Chapter3. The amidinometal complexes were applied to catalyze the Tishchenko reaction. High yields of carboxylic esters were obetained under optimalized conditions. We showed that the amidinolithium complexes and the amidino-alumium/zinc complexes are active pre-catalysts in the Tishchenko reaction, with good activity for the aryl aldehyde and aliphatic aldehydes, respectively.