Hydrogen TransFer Hydrogenation of Acetophenone by Ruthenium Complexes Containing Polydentate Aminophosphine Ligand

利用C2-对称的双胺双膦钌（Ⅱ）配合物ruCl2（P2n2H4）为催化剂，研究了苯乙酮的氢转移还原反应.在苯乙酮、钌配合物和异丙氧基钾的摩尔比为200∶1∶12的条件下，于65℃反应2H后，苯乙酮的转化率高达99%.讨论了苯乙酮的氢转移氢化机理.The catalytic hydrogen transFer hydrogenation of acetophenone using C 2 symmetric diamine/diphosphine ruthenium(Ⅱ) complex has been studied.Complex RuCl 2(P 2N 2H 4) shows an excellent catalytic activity in hydrogen transFer hydrogenation of acetophenone in a molar ratio of substrate/Ru/ iso PrOK 200∶1∶12, leading to 2 phenylethanol in 99% yield aFter 2 h.A hydrogen transFer mechanism is also discussed.国家自然科学基金;中国石油化学工业总公司石油化工科学院资

Synthesis, Characterization of New Palladium Complexes and Their Catalytic Properties to Hydrogenation Reaction

等摩尔的Pd（CH3Cn）2Cl2与邻-二苯基膦苯甲醛在乙醇中回流反应，生成了缩醛化膦配体配位的钯氯化物PdCl2｛PH2P［O-C6H4CH（OC2H5）2］｝2（I）.双亚胺双膦配体n，n′-双-［邻-（二苯基膦）苯亚甲基］乙二胺（简称P2n2）与1或2摩尔的Pd（CH3Cn）2Cl2在二氯甲烷中回流反应，分别高产率地制得PdCl2（P2n2）（I）和Pd2Cl2（P2n2）（II）.进行了元素分析、谱学表征或X射线结构分析.考察了这些配合物催化苯乙烯和丙烯酸的氢化.双核的钯配合物Pd2Cl2（P2n2）发挥了最高活性.The interaction of Pd(CH_3CN)_2Cl_2 and one equivalent of o(diphenylphosphino)benzaldehyde in refluxing ethanol gives transPdCl_2{Ph_2P(O-C_6H_4CH(OC_2H_5)_2)}_2 (I) in moderate yield.Mononuclear palladium complex PdCl_2(P_2N_2) (Ⅱ) could be prepared on high yield via the interaction of Pd(CH_3CN)_2Cl_2 and one equivalent of N, N′-bis(O-(diphenylphosphino) benzylidene)ethylenediamine(P_2N_2 for short) in refluxing dichloromethane.If two equivalent of Pd(CH_3CN)_2Cl_2 is used, a new dinuclear palladium complex Pd_2Cl_2(P_2N_2) (Ⅲ) will be formed.Complexes IIII have been fully characterized by elementary analysis and spectroscopic methods.The structure of complex I has been established by an Xray diffraction study.The complexes IIII as catalyst for homogeneous hydrogenation of styrene and acrylic acid have been investigated and the results indicate the dinuclear complex III is more effective catalyst.国家自然科学基金;中国石油化学工业总公司石油化工科学院资

Hydrogen transfer hydrogenation of acetophenone by ruthenium complexes containing polydentate aminophosphine ligand

The catalytic hydrogen transfer hydrogenation of acetophenone using C-2-symmetric diamine/diphosphine ruthenium(II) complex has been studied. Complex RuCl2(P2N2H4) shows an excellent catalytic activity in hydrogen transfer hydrogenation of acetophenone ina molar ratio-of substrate/Ru/iso-PrOK 200:1:12, leading to 2-phenylethanol in 99% yield after 2 h, A hydrogen transfer mechanism is also discussed