Synthesis And Reactivity Of Organometallic Complexes Based On Triamidoamine-type N-P Ligands

Triamidoamine-type ligands have attracted much attention in the field of organometallic chemistry due to their facile preparation,modification and formation of a"pocket-type"sterically protected structure.Over the past three decades,the chemistry with N-alkyl,-silyl,and-aryl substituted triamidoamine ligands has been rapidly developed,which includes the synthesis and reactivity of complexes containing main group elements,transition metals,lanthanide or actinide.However,phosphine-functionalized triamidoamine ligands have rarely been reported.On the other hand,frustrated Lewis pairs(FLPs)have been shown to activate of H₂in 2006,a large number of FLPs species have been synthesized and various catalytic conversions were revealed during the past decade.However,the synthesis routes of FLPs based on main group elements or transition metal are usually complicated,thus rare earth metal-based FLPs have been gradually reported.In this dissertation,the synthesis and reactivity of main group elements,lanthanide and actinide complexes with phosphine-functionalized novel triamidoamine ligand are studied,which consists of the following six chapters:In chapter 1,the concept and the type of tripod ligands are briefly introduced.The chemistry of triamidoamine-type ligands and FLP in main group elements,transition metals and f-block complexes are emphatically reviewed.Finally,research objectives and purposes of this dissertation are presented.In chapter 2,gallium complex with phosphine-functionalized triamidoamine ligand was synthesized and its structure was fully characterized.The gallium complex exhibited FLP-type reactivity with heteroallenes,phenylacetylene,(trimethylsilyl)diazomethane and[Ir Cl(COD)]₂,which led to the formation of a series of species with five-or four-membered heterocycle.In chapter 3,a novel cerium complex with a similar triamidoamine ligand was readily prepared by amine elimination method.The cerium complex displayed triple FLP-type reactivity with a series of heteroallenes,diazomethane and organic azides.Interestingly,the reaction of this Ce species with trimethylsilyl azide gave a Staudinger reaction product while reacts with 1-azidoadamantan can not liberate N₂even under heating condition.The reactivity of carbodiimide and CO₂ were also investigated.In chapter 4,triamidoamine-type uranium complexes with different substituted were synthesized and their catalytic property were investigated.The alkyl-and iodide-substituted uranium complexes were obtained through ligand substitution reaction.Alkyl complex could act as a pre-catalyst for the hydroboration of carbonyl substrates that displayed good tolerance for functional group.Aldehydes exhibited higher reactivity based on the competitive experiment result.In chapter 5,a cerium complex with 2-amidopyridine ligand was prepared by salt metathesis or amine elimination method.The cerium complex was treated with group10 metals to synthesize the heterobimetallic complexes,the structure of those complexes without axial donors were observed.It was shown that the structure was related to ligand and metal precursor.The interaction between cerium and transition metal in those complexes were investigated,which have broaden the family of heterobimetallic complexes.In chapter 6,the summary of this dissertation was showed and the prospect of the future research was also presented.