新的膦钯配合物的合成、表征及其催化氢化性能
Synthesis, Characterization of New Palladium Complexes and Their Catalytic Properties to Hydrogenation Reaction
Abstract
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.