1,1′-bis(phosphino)ferrocene ligands are commonly employed in a variety of catalytic systems. These ligands are of particular interest as the steric and electronic properties of the phosphorus donor atoms can be altered by changing the substituents of the phosphines. In addition, the ferrocene backbone of the ligands provides unique electronic and conformational flexibility to these ligands. Previous investigations in this lab have examined catalytic ring closing reactions using a series of gold compounds with bis(phosphino)ferrocene ligands, [Au₂Cl₂(μ-PP)]. These gold compounds were shown to react with sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, Na[BArF₂₄], to generate a cationic species with the general formula [Au₂(μ-Cl)(μ-PP)][BArF₂₄] that are much more efficient catalysts than the [Au₂Cl₂(μ-PP)] compounds. In this study, a series of [Au2Cl2(μ-PP)] (μ-PP = 1,1′-bis(diphenylphosphino)ferrocene (dppf), 1,1′-bis(diiso-propylphosphino)ferrocene (dippf), 1,1′-bis(dicyclohexylphosphino)ferrocene (dcpf), 1,1′- bis(ditert-butylphosphino)ferrocene (dtbpf), 1-diphenylphosphino-1′-ditert-butylphosphinoferrocene (dppdtbpf) or 1,1ʹ-bis(5-methyl-2-furanylphosphino)ferrocene (dfurpf)) compounds were examined as catalysts for the intramolecular ring-closing hydroamination of 3-(vinyloxy)propan-1-amine and the intermolecular hydroamination of phenylacetylene with a variety of phenylamine reagents. The catalytic activity of the corresponding [Au₂(μ-Cl)(μ-PP)][BArF₂₄] compounds that were generated in situ was also explored. Two new [Au2Cl2(μ-PP)] compounds with chiral bis(phosphino)ferrocene ligands (PP = 1,1′-bis(2R,5R-dimethylphospholanyl)ferrocene (R-d^Meplf) or 1,1′-bis(2S,5S-dimethylphospholanyl)ferrocene (S-d^Meplf)) were prepared, characterized spectroscopically and electrochemically, and evaluated as catalysts in the ring-closing hydroamination reaction. In addition, the X-ray structures of [Au2Cl2(μ-PP)] (PP = dppdtbpf, R-d^Meplf and S-d^Meplf) were determined.

1,1'-双（膦基）二茂铁配体通常用于各种催化体系中。这些配体特别受关注，因为磷供体原子的空间和电子性质可以通过改变膦的取代基来改变。此外，配体的二茂铁骨架为这些配体提供了独特的电子和构象柔韧性。该实验室以前的研究已经研究了使用一系列具有双（膦）二茂铁配体[Au ₂ Cl ₂（μ-PP）]的金化合物催化的闭环反应。这些金化合物已显示出与四（3,5-双（三氟甲基）苯基）硼酸钠Na [BArF ₂₄ ]反应，生成具有通式[Au ₂（μ-Cl）（μ-PP）] [BArF ₂₄ ]是比[Au ₂ Cl ₂（μ-PP）]化合物更有效的催化剂。在这项研究中，一系列[Au2Cl2（μ-PP）]（μ-PP = 1,1'-二（二苯基膦基）二茂铁（DPPF），1,1'-双（二异-propylphosphino）二茂铁（dippf） ，1,1'-双（二环己基膦基）二茂铁（dcpf），1,1'-双（二叔丁基膦基）二茂铁（dtbpf），1-二苯基膦基-1'-di tert研究了丁基丁基二茂铁（dppdtbpf）或1,1′-双（5-甲基-2-呋喃基膦基）二茂铁（dfurpf））化合物作为3-（乙烯基氧基）丙-1-胺分子内闭环加氢胺化反应的催化剂。用各种苯胺试剂进行苯乙炔的分子间加氢胺化。还探讨了原位生成的相应[Au ₂（μ-Cl）（μ-PP）] [BArF ₂₄ ]化合物的催化活性。具有手性双（膦）二茂铁配体（PP = 1,1'-双（2R，5R-二甲基磷杂环戊基）二茂铁（Rd ^Me plf）或1,1'-双（2S）的两种新的[Au2Cl2（μ-PP）]化合物，5S-二甲基磷杂环戊烷基）二茂铁（S -d ^Me制备ppl）），对其进行光谱学和电化学表征，并评价为在闭环加氢胺化反应中的催化剂。另外，确定了[Au 2 Cl 2（μ-PP）]的X射线结构（PP ＝ dppdtbpf，Rd ^Me plf和S -d ^Me plf）。