Hybrid phosphines usually combine a phosphine moiety with another heteroatom secondary donor group in their structures while compounds equipped with hydrocarbyl π–donor moieties remain uncommon. This contribution reports the synthesis and structural characterization of the first P/π-allyl-chelating complexes that were obtained using the structurally flexible and redox-active ferrocene unit as the scaffold, viz. [PdCl(R₂PfcCHCHCH₂-η³:κP)] (1^R; R = Ph and cyclohexyl (Cy); fc = ferrocene-1,1′-diyl). These compounds were synthesized from the respective phosphinoferrocene carboxaldehydes R₂PfcCHO via reaction with vinylmagnesium bromide to generate 1-(phosphinoferrocenyl)allyl alcohols, which were subsequently acetylated. The resulting allyl acetates reacted smoothly with [Pd₂(dba)₃]/[Et₃NH]Cl (dba = dibenzylideneacetone) to produce the target compounds. Complexes 1^R and their nontethered analogues [PdCl(η³-C₃H₅)(FcPR₂-κP)] (5^R; Fc = ferrocenyl) were evaluated as pre-catalysts for the Pd-catalysed allylic amination of cinnamyl acetate with aliphatic amines and Suzuki–Miyaura-type cross-coupling of 4-tolylboronic acid with benzoyl chloride. In these reactions, better results were achieved with compounds 5^R (particularly with 5^Ph), presumably because they form more stable LPd(0)-type catalysts.

中文翻译：

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P,π-螯合二茂铁膦烯丙基配体及其非束缚类似物的钯(II)配合物的合成和催化性能

杂化膦通常在其结构中将膦部分与另一个杂原子二级供体基团结合，而配备烃基π供体部分的化合物仍然不常见。该贡献报告了第一个 P/π-烯丙基螯合配合物的合成和结构表征，该配合物是使用结构灵活且具有氧化还原活性的二茂铁单元作为支架获得的，即。 [PdCl(R ₂ PfcCHCHCH ₂ -η ³ :κ P )] ( 1 ^R；R = Ph 和环己基 (Cy)；fc = 二茂铁-1,1′-二基)。这些化合物是由各自的膦基二茂铁甲醛R ₂ PfcCHO与乙烯基溴化镁反应合成的，生成1-(膦基二茂铁基)烯丙醇，随后将其乙酰化。所得乙酸烯丙酯与[Pd ₂ (dba) ₃ ]/[Et ₃ NH]Cl（dba=二亚苄基丙酮）顺利反应生成目标化合物。配合物1 ^R及其非束缚类似物 [PdCl(η ³ -C ₃ H ₅ )(FcPR ₂ -κ P )] ( 5 ^R ; Fc = 二茂铁基) 作为 Pd 催化乙酸肉桂酯烯丙胺化的预催化剂进行了评估与脂肪胺和 4-甲苯基硼酸与苯甲酰氯的 Suzuki-Miyaura 型交叉偶联。在这些反应中，化合物5 ^R（特别是5 ^Ph）取得了更好的结果，大概是因为它们形成了更稳定的 LPd(0) 型催化剂。