二茂铁烯丙基卡宾钯络合物的合成及催化性能

Synthesis and Catalytic Properties of [(N-Heterocyclic carbene) Pd (ferrocenyl-allyl) Cl]

摘要:

采用一锅法将咪唑盐对二茂铁烯丙基钯二聚体I在室温下进行解聚，避免了使用不稳定的卡宾，简便、高效地合成了二茂铁烯丙基卡宾钯络合物II。通过IR，1H NMR，13C NMR，MS，HRMS和X射线单晶衍射对其结构进行鉴定。络合物II对空气和湿气稳定，且对芳基氯代物参与的Suzuki-Miyaura 偶联反应和Buchwald-Hartwig胺化反应展现较高的催化活性。在反应温度70 oC，0.4 mol％络合物II催化芳基氯代物与芳基硼酸的偶联反应时，取得95-100%收率；在反应温度100 oC，0.5 mol％钯络合物II催化氯苯与多样化胺的偶联反应时，也获得中等至好的的收率。

Abstract:

[(N-Heterocyclic carbene)Pd(ferrocenyl-allyl)Cl] II was prepared easily in good yield by simple addition of THF solution of 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride (IPrHCl) to chloride-bridged ferrocenyl-allyl-Pd dimer I at room temperature. The one-pot synthesis avoids multi-step reactions employing free carbene. Complex II was characterized by IR, 1H NMR, 13C NMR, MS and HRMS. Additionally, the detailed structure has been determined by single-crystal X-ray analysis. Complex II was stable to air and moisture, and displayed high catalytic activities for the Suzuki-Miyaura coupling reaction of a variety of aryl chlorides with aryl boronic acids with catalyst loadings of 0.4 mol % at 70 oC, and the Buchwald-Hartwig amination of chlorobenzene with various amines in the presence of 0.5 mol% complex II at 100 oC.