诚信声明我声明，所呈交的毕业论文（设计）是本人在老师指导下进行的研究工作及取得的研究成果。据我查证，除了文中特别加以标注和致谢的地方外，论文（设计)中不包含其他人已经发表或撰写过的研究成果，也不包含为获得其他教育机构的学位或证书而使用过的材料。我承诺，论文（设计）中的所有内容均真实、可信。毕业论文（设计）作者（签名）：◇年月C(sp)-H酰胺化反应的镍氮宾形成及氢提取机理研究【摘要】目的：过渡金属催化C(sp)一H酰胺化形成碳氮键的反应一直是具有挑战且热门的研究领域，该类反应为形成C一N键提供了更为直接高效的方式。本论文针对金属配合物[(Bc)Ni](C10,)2催化C(sp)一H酰胺化反应，研究反应中形成金属氮宾和氢提取的机理，为后续高效合成酰胺化产物提供重要信息。方法：本论文运用密度泛函理论的B3LYP泛函的计算方法，对反应所涉及的反应物、中间体及过渡态进行结构优化和频率分析。结果：双2,9-二甲基-1,10-菲啰啉配体的镍金属配合物无法与二氧恶唑酮形成相互作用：镍氮宾前期复合物通过同时断裂N-0键和C-0键而释放二氧化碳形成镍氮宾的活化能为16.4kca/mol;镍氮宾在四氢呋喃(THF)氧原子的邻位上进行氢提取的活化能为18.3 kcal/mol,并且与底物上的氧原子形成2个氢键，间位上氢提取的活化能为25.3 kcal/mol,与底物上的氧原子形成1个氢键。结论：镍催化剂前体发生2,9-二甲基-1,10菲啰啉配体解离：氢提取选择性地在底物氧原子的邻位上发生，与形成氢键有关，为整个酰胺化反应的决速步骤。【关键词】酰胺化：镍催化：氮宾：C0,释放：氢提取Mechanism of the Formation of Ni-nitrenoid and Hydrogenatom extraction in C(sp3)-H Amination Reaction[Abstract]Purpose:The reaction of transition metals catalyzed the Amination ofC(sp3)-H bonds to form carbon-nitrogen bonds has been a challenging and hotresearch area.This type of reaction provides a more direct and efficient way to formC-N bonds.This paper focuses on the formation of metal-nitrenoid and hydrogenextraction in nickel-catalyzed C(sp)-H amidation reaction,and further studies themechanism of nickel-catalyzed C(sp3)-H amidation reaction,providing importantinformation for subsequent experiments.Methods:In this paper,the B3LYPfunctional calculation method of density functional theory is used to geometricallyoptimize the reactants,intermediates and transition state that involved in the researchof nickel-catalyzed C(sp)-H amidation reaction,and to conduct frequency analysis.Result:The metal compound with bis (2,9-dimethyl-1,10-phenanthroline)ligand wasunable to interact with dioxazolone.The activation energy of nickel-nitrenoidprecursor complex,which releases carbon dioxide by simultaneously breaking N-Oand C-O bonds,to form nickel-nitrenoid is 16.4 kcal/mol.The activation energy forhydrogen extraction at the ortho-position of tetrahydrofuran (THF)is 18.3 kcal/mol,and they form two hydrogen bonds with the oxygen atom.The activation energyrequired for hydrogen extraction at the meta-position is 25.3 kcal/mol,and they formone hydrogen bond.Conclusion:The precursor of nickel catalyst undergoes liganddisxxiation of 2,9-dimethyl-1,10-phenanthroline.Hydrogen extraction selectivelyoccurs adjacent to the oxygen atom,which is related to the formation of hydrogenbonds and is the rate-determining step in the entire amidation reaction.[Keywords]Amidation Ni catalysis Nitrene release CO2;Hydrogen atomextraction