【作者】 刘洋；

【导师】 郭放；

【作者基本信息】 辽宁大学 ， 有机化学（专业学位）， 2023， 硕士

【摘要】 金属有机化合物结构多样新颖,可以用于催化、分子开关、以及电化学等领域。本文以含有卡宾碳苯并咪唑吡啶功能化的鎓盐配体与金属盐反应生成两种类型的物质,一种是金属有机盐,即有机配体阳离子与卤化金属阴离子通过静电引力相结合的有机-无机杂化化合物,另外一种是通过金属与苯并咪唑鎓盐中的卡宾碳配位而形成的络合物,即氮杂环卡宾配合物。硫醚化合物是常见药物分子或者食品分子的中间体,C-S键是构建硫醚化合物的关键步骤。已报道的C-S偶联产物一般需要在含钯、钌等贵金属催化剂存在下,二氯乙烷等有机试剂较高温度回流下才能得到产物,反应时间长、违背可持续发展理念与绿色化学原则。相对于溶液法合成,机械化学利用机械力诱发和促进反应的快速高效进行,是一种绿色高效的方法。本文采用吡啶功能化的苯并咪唑鎓盐作为配体,采用溶液法和机械化学技术合成系列氮杂环卡宾配合物及其金属有机盐,并应用于C-S交叉偶联反应。首先通过压力管110℃高温合成苯并咪唑氯盐[H₂L]Cl₂,（[H₂L]=3,3’-（1,2-双亚甲基苯基）双-1-（吡啶-2-甲基）-1H-苯并[d]咪唑）,然后与MX₄（M=Cu、Co、Cd,X=Cl、Br）机械研磨分别得到了金属有机盐[H₂L]²⁺[Cu Cl₄]^2-（1）、[H₂L]²⁺[Co Cl₄]^2-（2）、[H₂L]²⁺[Cd Br₄]^2-（3）、[H₄L]⁴⁺[CoCl₄]^2-2Cl^-·CH₃CN（4）。通过单晶衍射、粉末衍射等对结构进行了表征,通过Crystal Explorer和XPac等计算软件对金属有机盐1-4结构相似程度进行了系统分析。[H₂L]Cl₂与NH₄PF₆进一步机械研磨得到[H₂L]（PF₆）₂,随后与Ni（OAc）₂·4H₂O在溶液中70℃恒温反应2 h得到配合物[Ni L]（PF₆）₂·CH₃CN（5）,将配合物5与Na I在溶液中反应3 h,成功置换阴离子得到配合物[Ni L]I₂·CH₃CN（6）与[Ni L]I₂·CH₃CN（6′）。[H₂L]Cl₂与Na I反应可以生成[H₂L]I₂,与Ni（OAc）₂·4H₂O在溶液中70℃恒温反应2 h得到配合物[Ni L]I₂·CH₃CN（6）。以上化合物通过X-射线单晶衍射仪、PXRD粉末衍射仪以及红外光谱、核磁共振谱进行表征。选用上述化合物作为催化剂应用于C-S偶联反应催化。2-溴苯乙酮与2-巯基苯并噻唑作为C-S反应的底物,结果表明,配合物5的催化效果最佳,通过优化催化剂用量、液体辅助研磨种类、研磨时间等因素,得到最佳条件为0.25 mol%的配合物5加入90μL的N,N-二甲基甲酰胺（DMF）溶液辅助球磨20 min后,C-S偶联催化产率可达95%。在最佳条件的基础上,进一步探究了底物的适用性,发现无论是被给电子基还是吸电子基所取代的2-溴苯乙酮都可以达到中等及以上的产率,体现了配合物5作为催化剂有良好的催化效果。更多还原

【Abstract】 Metal organic compounds have diverse and novel structures,and can be used in fields such as catalysis,molecular switching,and electrochemistry.This article uses onium salt ligands containing carbene carbon functionalized with benzimidazolium pyridine to react with metal salts to generate two types of substances.One is a metal organic salt,which is an organic-inorganic hybrid compound formed by the combination of organic ligand cations and halogenated metal anions through electrostatic attraction.The other is a complex formed by the coordination of metal with carbene carbon in benzimidazolium salt,which is a nitrogen heterocyclic carbene complex.Sulfide compounds are common intermediates of drug or food molecules,and the C-S bond is a key step in constructing sulfide compounds.The reported C-S coupling products generally require the presence of palladium,ruthenium and other noble metal catalysts,and the reflux of organic reagents such as dichloroethane at high temperatures to obtain the products.The reaction time is long,which violates the concept of sustainable development and the principle of green chemistry.Compared to solution synthesis,mechanochemistry utilizes mechanical forces to induce and promote rapid and efficient reactions,making it a green and efficient method.In this paper,pyridine functionalized benzimidazolium salts were used as ligands to synthesize a series of N-heterocyclic carbene complexes and their organometallic salts by solution method and mechanochemical techniques,and were applied to C-S cross coupling reaction.Firstly,benzimidazole chloride salt [H₂L]Cl₂（[H₂L] = 3,3’-（1,2-bismethylenephenyl）bis-1-（pyridin-2-methyl）-1H-benzo[d]imidazole）was synthesized at a high temperature of 110℃ under a pressure tube,and then mechanically ground with MX₄（M = Cu,Co,Cd,X = Cl,Br）to obtain four metalorganic salts [H₂L]2+[Cu Cl4]2-（1）,[H₂L]₂+[CoCl₄]₂-（2）,[H₂L]²⁺[CdBr₄]2-（3）,[H₄L]⁴⁺[CoCl₄]²-2Cl^-·CH₃CN（4）.The structure was characterized by single crystal diffraction,powder diffraction,etc.,and the similarity of the structure of metal organic salt 1-4 was systematically analyzed using calculation software such as Crystal Explorer and XPac.[H₂L]Cl₂ and NH₄PF₆ were further mechanically ground to obtain [H₂L]（PF₆）₂.Subsequently,the complex [Ni L]（PF₆）₂·CH3CN（5）was obtained by reacting with Ni（OAc）₂·4H₂O in a solution at 70 ℃ for 2 h.The complex 5 was reacted with Na I in the solution for 3 h,successfully replacing anions to obtain the complexes[Ni L]I2·CH3CN（6）and [Ni L]I2·CH3CN（6’）.The reaction of [H₂L]Cl₂ with Na I can generate [H₂L]Cl₂,and the complex [NiL]I₂·CH₃CN（6）is obtained by reacting with Ni（OAc）₂·4H₂O in a solution at 70 ℃ for 2 h.The above compounds were characterized by X-ray single crystal diffraction,PXRD powder diffraction,infrared spectroscopy,and nuclear magnetic resonance spectroscopy.The above compounds were selected as catalysts for C-S coupling reaction.Phenylacetyl bromide and benzothiazole mercaptan were used as substrates for the CS reaction.The results showed that the catalytic effect of complex 5 was the best.By optimizing factors such as catalyst dosage,liquid assisted grinding type,and grinding time,After obtaining the optimal condition of 0.25 mol% complex 5 and adding 90 μL of N,N-dimethylformamide（DMF）solution to assist ball milling for 20 minutes,the catalytic yield of C-S coupling can reach 95%.On the basis of the optimal conditions,the applicability of the substrate was further explored,and it was found that phenylacetyl bromide,whether replaced by electron donating or electron withdrawing groups,can achieve moderate or higher yields,reflecting the good catalytic effect of complex 5 as a catalyst.更多还原