【作者】 杨小平；

【导师】 陈金龙；

【作者基本信息】 南昌大学 ， 化学工程与技术， 2025， 硕士

【摘要】 钳型配体因容易合成、稳定性高和结构易于调节而成为有机配体的重要种类之一。钳型金属配合物具有可定制的配位环境和良好的热稳定性,因此在众多均相催化反应中表现出广泛的适用性。本论文通过配体设计,制备了一系列钳型镍配合物,其中PN³P-钳型镍硝酸根配合物表现出良好的光反应性质,硝酸根通过氧原子转移生成一系列新的钳型镍化合物;而含有苯基和磷位点的吡啶配体,可以通过C-H活化生成PNC-钳型镍配合物,所得产物可以发生一系列转化。（1）通过配合物的后功能化改性制备了稳定性良好的PN³P-钳型镍氯化物1（PN³P-Ni Cl）,1与硝酸银发生复分解反应制得了PN³P-钳型镍硝酸根配合物2（PN³P-Ni NO₃）,它在300W氙灯照射下通过氧原子转移生成了钳型镍硝基配合物3（PN³P-Ni NO₂）、4[PN³P（O）-Ni NO₂]和配体磷原子完全氧化的镍二硝酸根配合物5[P（O）N³P（O）-Ni（NO₃）₂];并用核磁和单晶等分析手段确定了2-5的结构。实验结果表明,改性的PN³P-配体对稳定[Ni NO₃]有着重要作用,该研究对土壤和大气中的硝酸根离子的还原具有一定理论意义。（2）设计合成了N-二叔丁基膦-6-苯基吡啶-2-胺配体,它与不同的镍前体反应时得到了结构完全不同配合物。配体与双（1,5-环辛二烯）镍反应会生成吡啶环3号位发生C-H活化的镍烯丙基配合物6（PC-Ni COE）,此时苯基和吡啶氮原子都未参与反应或配位;而该配体与二氯化镍乙二醇二甲醚反应时,则生成N、P原子双齿配位的镍二氯化物7（PN-Ni Cl）,该配合物在1当量叔丁醇钾的作用下会生成苯环2号位发生C-H活化的PNC-钳型镍单氯配合物8（PNC-Ni Cl）,配合物8在另一当量叔丁醇钾和一氧化碳的作用下则进一步转化为吡啶环去芳香化的PNC-钳型镍羰基化合物9（PNC-Ni CO）.根据实验结果,我们提出了生成各种配合物的反应机理。该部分内容对研究吡啶基钳型镍配合物的金属-配体协同作用和C-H活化反应具有一定的指导作用。更多还原

【Abstract】 Pincer-type ligands have become one of the most important organic ligands due to their easy synthesis,high stability,and easily adjustable structure.Pincer-metal complexes have tailorable coordination environments and good thermal stability,making them widely applicable in numerous homogeneous catalytic reactions.This thesis prepared a series of pincer-nickel complexes through ligand design,among which the PN³P-pincer type nickel nitrate complex exhibited excellent photochemical reaction properties and could generate a series of new nickel nitrate and nitro complexes through oxygen atom transfer under irradiation conditions.Pyridine ligands containing phenyl and phosphine moiety can form PNC-nickel pincer complex through C-H activation,the resulting complex can achieve a series of transformations under different experimental conditions.（1）The thermal stable PN³P-pincer type nickel chloride 1（PN³P-Ni Cl）was prepared by post-modification of the corresponding complex.PN³P-nickel nitrate complex 2（PN³P-Ni NO₃）was obtained by the metathesis of 1 and silver nitrate.Under the irradiation by a 300W xenon lamp（λ>250nm）,complex 2 underwent an oxygen atom transfer reaction to generate a series of pincer-type nickel nitro complexes 3（PN³P-Ni NO₂）and 4[PN³P（O）-Ni NO₂],and nickel dinitrate complex 5[P（O）N³P（O）-Ni（NO₃）₂].The structures of complexes 2-5 were confirmed by NMR and X-ray single crystal diffraction analyses.The experimental results indicate that a stable PN³P-ligand skeleton plays an important role in studying the decomposition of nitrate ions,and this study has certain theoretical significance for the reduction of nitrate ions in soil and atmosphere.（2）The N-（di-tert-butylphosphaneyl）-6-phenylpyridin-2-amine ligand was designed and synthesized.It reacted with different nickel precursors to produce nickel complexes with discriminated structures.The ligand reacted with bis（1,5-cyclooctadiene）nickel to form a nickel allyl complex 6（PC-Ni COE）through C-H activation at the C3 position of the pyridine ring,in which neither the phenyl nor pyridine nitrogen atom participates in the reaction,when the ligand reacted with Ni Cl₂.DME to afford the N-and P-coordinated nickel dichloride 7（PN-Ni Cl）,which generated a PNC-pincer nickel chloride complex 8（PNC-Ni Cl）through C-H activation at the C2 position of the benzene ring under the action of potassium tert-butoxide.Complex 8 was further converted into a PNC-nickel carbonyl compound 9（PNC-Ni CO）accompanied by pyridine ring dearomatization under the action of another potassium tert-butoxide and carbon monoxide.Based on the experimental results,we elucidated the reaction pathways of various complexes and proposed the possible reaction mechanisms.This study guides investigating the metal-ligand cooperation and C-H activation of pyridine-based nickel complexes.更多还原