New Chiral Palladium(0) and -(II) Complexes of (Aminoferrocenyl)phosphine Ligands PPFA and PTFA. X-ray Crystal Structure Analysis and Fluxional Behavior Involving Alkene Rotation, Pd−N Bond Rupture, and Selective η3−η1−η3 Allyl Isomerization
New Chiral Palladium(0) and -(II) Complexes of (Aminoferrocenyl)phosphine Ligands PPFA and PTFA. X-ray Crystal Structure Analysis and Fluxional Behavior Involving Alkene Rotation, Pd−N Bond Rupture, and Selective η3−η1−η3 Allyl Isomerization
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(氨基二茂铁基)膦配体 PPFA 和 PTFA 的新型手性钯 (0) 和 -(II) 配合物 PPFA 和 PTFA
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发表时间：
1997
期刊：
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通讯作者：
G. Jogl
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作者：
Rafael Fernández;F. A. Jalón;B. Manzano;Jerónimo Rodríguez;Miranda Vrahami;B. Jedlicka;W. Weissensteiner;G. Jogl
用(氨基二茂铁基)膦配体2-(1-(dimethylamino)ethyl)-1-(diphenylphosphino)ferrocene(PPFA)和[η5-cyclopentadienyl][η5-4-(endo-dimethylamino)-3-(diphenylphosphino)-4，5，6，7-tetrahydro-1H-indenyl]iron(II)(PtFA)作为钯(0)和-(II)配合物的配体。Pd2(Dba)3·CHCl3与PPFA或PTFA在吸电子的马来酸酐(MA)和富马酸二甲酯(DMFU)存在下反应生成Pd(PTFA)(DMFU)(2)、Pd(PPFA)(MA)(3)和Pd(PPFA)(DMFU)(4)。在AgTf存在下，将η或Pd(η3-2-Me-C3H4)与[Pd(η3-2-Me-C3H4)Cl]2反应，得到了[Pd(Pd3-2-Me-C3H4)]Tf(5)和[Pd(Pd(PPFA)3-Me-C3H4)]Tf(6)(Tf=三氟酸根)。在溶液中，所有这些化合物都以两个非对映异构体的混合物形式存在，其中烯基或烯丙基相对于氨基膦配体有不同的取向。对2-−-6和Pd(PTFA)(MA)(1)进行了~1H核磁共振变温研究。此外，还观察到了烯烃的旋转性。
(Aminoferrocenyl)phosphine ligands 2-(1-(dimethylamino)ethyl)-1-(diphenylphosphino)ferrocene (PPFA) and [η5-cyclopentadienyl][η5-4-(endo-dimethylamino)-3-(diphenylphosphino)-4,5,6,7-tetrahydro-1H-indenyl]iron(II) (PTFA), were used as ligands in palladium(0) and -(II) complexes. The reaction of Pd2(dba)3·CHCl3 with PPFA or PTFA in the presence of the electron-withdrawing olefins maleic anhydride (MA) and dimethyl fumarate (DMFU) gave the complexes Pd(PTFA)(DMFU) (2), Pd(PPFA)(MA) (3), and Pd(PPFA)(DMFU) (4). Allylic complexes [Pd(η3-2-Me-C3H4)(PTFA)]Tf (5) and [Pd(η3-2-Me-C3H4)(PPFA)]Tf (6) (Tf = triflate) were obtained by reaction of PTFA or PPFA with [Pd(η3-2-Me-C3H4)Cl]2 in the presence of AgTf. In solution all these compounds exist as mixtures of two diastereomers, with either the alkene or the allyl group differently oriented with respect to the aminophosphine ligand. 1H NMR variable-temperature studies have been carried out for 2−6 and for Pd(PTFA)(MA) (1). Rotation of the alkene was observed for com...