【作者】 俞丙然；

【导师】 唐宁； 席婵娟；

【作者基本信息】 兰州大学 ， 无机化学， 2010， 硕士

【摘要】 近年来,采用膦配位的过渡金属配合物催化C-C键偶联和C-N键偶联反应已经成为了现代化学研究的热点之一。其中钯、钌催化的偶联体系是优良的又有应用前景的催化体系。从经济性和制备的简易性考虑,用催化剂量的过渡金属配合物替换化学计量的金属有机试剂势在必行。相比于传统强碱条件对底物基团的限制,过渡金属配合物催化的反应可以在更广的催化条件下使用。本论文合成了含有大位阻和富电子膦配体的1,2-二芳基乙烯基钯(Ⅱ)、钌(Ⅱ)配合物。通过元素分析、质谱、红外光谱、1H NMR、13C NMR、31P NMR、X-射线单晶衍射等分析方法,研究了配合物的组成、结构并考察了这些配合物在不同催化体系中(Suzuki-Miyaura反应、胺芳基化偶联、C-H活化)对芳基卤代苯加成催化的效果。结果显示,乙烯基膦配体L1-L3和乙烯基膦钯(Ⅱ)、钌(Ⅱ)配合物C1-C9均能在空气中稳定存在；配合物C1-C6在Suzuki-Miyaura和胺芳基化偶联反应中均表现出很高的催化活性；配合物C7-C9在催化取代氯苯和2-芳基吡啶衍生物邻位芳基化的偶联反应中表现出很高的催化活性,且表现出出色的化学选择性。本论文由四部分组成：一、概述了各类含膦钯配合物催化剂在Suzuki-Miyaura和C-N偶联反应中及膦钌配合物在C-H活化偶联反应的发展应用。二、设计合成了三个1,2-二芳基乙烯基膦配体L1-L3。并利用转金属方法制备、表征了(Z)-[(3-二苯基膦)(2,3-二苯基丙烯基)]二羰基(甲基环戊二烯)钨。三、设计合成了1,2-二芳基乙烯基膦钯配合物C1-C6。其中配合物C1-C3是由氯桥连接的配体处于反式构型二聚配合物。而配合物C4-C6是2个膦配体和一个钯中心原子配位的化合物。所有配合物C1-C6在Suzuki-Miyaura和胺芳基化偶联反应中均表现出很高的催化活性和广泛的底物普适性。四、设计合成了1,2-二芳基乙烯基膦钌配合物C7-C9。配合物(1,2-二苯基)乙烯膦-(η6-对甲基异丙苯)RuCl2 (C7)的分子结构得到了X-射线单晶衍射的表征。所有的乙烯基膦钌配合物C7-C9可以控制催化2-苯基吡啶和氯苯偶联得到单取代和二取代的产物。实验数据表明,以配合物C7为例在催化富电子或缺电子氯苯和2-芳基吡啶衍生物邻位芳基化的偶联反应中表现出出色的催化活性。更多还原

【Abstract】 During the past years, the interest in complexes of transition metals with organophosphorus ligands has been growing considerably in light of their versatile applications in the coordination chemistry and homogenerous catalysis.The palladium and ruthenium system has a good prospects in the catalytic application. Preparative and economic advantages are expected from replacing such stoichiometric metalation reactions by catalytic ones. Particularly for a lack of selectivity under classic conditions or for base sensitivity of the functional groups, transition metal catalysis under mild and neutral conditions offers a promising and superior alternative. A series of (1,2-diaryl)vinylphosphine ligands (L1-L3) which have one aryl group at theα-position and one aryl group atβ-position on vinylphosphine to make the ligand more steric hindrance and electron-richness around the phosphorus atom were designed and synthesized. All of the ligands (L1-L3) and complexes (C1-C3) were synthesized and characterized by EA, MS, IR,1H NMR,13C NMR,31P NMR, and X-ray diffraction. The catalytic properties of some complexes on selective Aryl halides have been tested and employed in different cross coupling reactions, such as Suzuki reaction, arylamination reaction, C-H bond functionalization. As the catalytic results, all the complexes of palladium-(1,2-diaryl)vinylphosphine (C1-C6) as a catalyst show highly catalytic activity in Suzuki reaction and arylamination reaction; Ruthenium-(1,2-diaryl)vinylphosphine (C7-C9) complexes are highly efficient catalysts for direct ortho arylation of 2-arylpyrindine with different types of aromatic chlorides. Highyl controllable formation of monoarylation and diarylation through functionalization of C-H bonds on the aromatic ring can be observed.This thesis consists of four parts:1. The recent advances about the studies in the catalytic Suzuki coupling reaction and C-N coupling reaction by palladium; the catalytic C-H activation reaction by ruthenium were reviewed. 2. A series of (1,2-diaryl)vinylphosphine ligands were designed and synthesized. Synthesis and characterization of (Z)-[(3-diphenylphosphino)(2,3-diphenylpropenoyl)]dicarbonyl(methylcyclopentadie nyl)tungsten under transmetalations reaction.3. A series of (1,2-diaryl)alkenylphosphine palladium complexes have been desired and synthesized. The complexes C1-C3 adopt a transoid conformation and exist as a chlorinebridged dimer. In complex C4-C6, the palladium atoms are coordinated by two molecules of alkenylphosphine and two chlorine atoms in a square-planar fashion. The two alkenylphosphines are arranged in trans to each other. For complex C4, it appears as twin-complex in solid. All the complexes as a catalyst show highly catalytic activity in Suzuki reaction and arylamination reaction.4. A series of (1,2-diaryl)vinylphosphine ruthenium complexes were designed and synthesized. The structure of (1,2-diphenyl)vinylphosphine-(η6-cymene)RuCl2 complex (C7) was confirmed by X-ray crystallography. Ruthenium-(1,2-diaryl)vinylphosphine (C7-C9) complexes are highly efficient catalysts for direct ortho arylation of 2-arylpyrindine with a range of electron-rich and electron-poor aromatic chlorides. Highyl controllable formation of monoarylation and diarylation through functionalization of C-H bonds on the aromatic ring can be observed.更多还原