新型胺膦钌配合物均相催化官能团烯烃的氢化

Homogeneous hydrogenation of functionalized olefins over a new diaminodiphosphine ruthnium (Ⅱ) complex

等摩尔的ＲｕＣｌ２（ＤＭＳＯ）４和Ｐ２Ｎ２Ｈ４｛Ｐ２Ｎ２Ｈ４＝Ｎ，Ｎ＇－双［邻－（二本基膦）苯甲基］乙二胺｝在四氢呋喃中回流反应，高产率地合成了新型胺膦钌配合物ＲｕＣｌ２（Ｐ２Ｎ２Ｈ４）。进行了元素分析和谱学表征。在温度４０～１００℃和氢压３。～５．０ＭＰａ下，该配合物是均相催化α，β－不饱和酸、芳香醛、糖醛和环已酮选择氢化的有效催化剂。研究了添加促进剂ＮＨ４ＰＦ６、ＡｇＮＯ３和Ｅｔ３Ｎ等对氢化反应的效应，讨论了氢化反应的机理。

The interaction of RuCl2(DMSO)4 and 1equivalent of N,N'-bis-[o-(diphenylphosphino) benzyl] ethylene-diamine,i. e.P2N2H4, inrefluxing tetrahydrofuran gives a new diaminodiphosphine ruthenium (Ⅱ) complex, RuCl2(P2N2H4), in high yield. Elemental analysisand spectroscopic characterization are carriedout for the new complex. At a reaction temperature of 30￣100℃ and a hydrogen pressure of 3. 0-5. 0MPa, the complex is found tobe an efficient catalyst for homogeneous selective hydrogenation of functionalized olefinssuch as α, β-unsaturated acids, aromatic aldehydes, furfural, and cyclohexanone. Effect ofadding NH4PF6, AgNO3, or Et3N as promotors on hydrogenation is also investigated, andthe mechanism of hydrogenation discussed.