Synthesis And Characterization Of Novel Pd(Ⅱ),Ru(Ⅱ) Complexes With Vinylphosphine And The Application In Cross Coupling Reaction

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.