Rare Earth Complexes With The Nh Bond Activation Of Unsaturated Organic Molecules

There is a currently considerable interest in studying the activity of organolanthanides on organic unsaturated small molecules,because these studies can serve as organic synthesis and provide some new strategies to synthesize novel organolanthanide complexes.The thesis focus mainly on investigating the addition of the N-H bonds of organolanthanide derivatives with organic unsaturated small molecules.Moreover,we also investigated on the synthesis and structures of organolanthanide derivatives with the guanidinoacetamidinate ligands.Herein,we synthesized twenty-six new organolanthanide complexes,and their structures were determined through X-ray single crystal diffraction analysis.This thesis is composed of four chapters.In ChapterⅠ,preface,the insertion chemistry of organolanthanides to some organic small molecules such as isocyanate/isothiocyanate,carbon dioxide/carbon bisulfide,ketene,and carbodiimide is introduced.In ChapterⅡ,we investigated a new organolanthanide-mediated intermolecular nucleophilic addition/cyclization of anthranilonitrile through 1,3-hydrogen shift to construct a novel 4-aminoquinazolinate anionic ligand.Further investigations on the scope of this addition/cyclization indicate that the N-H bonds of the intermediate Cp₂Ln(NHC₆H₄CN-2) can add to the C=N bond of carbodiimide molecule,and provide some effective methods for the construction of a novel bis-functional ligand [2-NCC₆H₄N=C(NHⁱPr)NⁱPr]^-.In ChapterⅢ,we investigated the synthesis of organolanthanide derivatives bearing the benzophenon hydrazonido(1-) ligand as well as their reactivity toward some unsaturated small molecules,indicating that PhNCO and PhCN can formally mono-insert into the N-H bond of these organolanthanide hydrazonido(1-) complexes,while PhNCS can only insert the lanthanide-nitrogen bond.In ChapterⅣ,we have synthesized eleven new organolanthanide complexes containing the guanidinoacetamidinate ligands[(RN)₂C(N=C(NMe₂)₂)]^- with versatile bonding modes.Moreover,an unusual hydrogen-abstraction to form neutral guanidinoacetamidine ligand has been found.