1,1'-bis(diethylphosphino)ferrocene | 191665-95-9

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: 1,1'-bis(diethylphosphino)ferrocene
• 英文别名: depf；Cyclopenta-1,3-dien-1-yl(diethyl)phosphane;iron(2+)；cyclopenta-1,3-dien-1-yl(diethyl)phosphane;iron(2+)
• CAS: 191665-95-9
• 化学式: C₁₈H₂₈FeP₂
• 分子量: 362.215
• InChiKey: BCPVFKXAPLQYIE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  dichloro(cycloocta-1,5-diene)palladium (II) 、 1,1'-bis(diethylphosphino)ferrocene 以 二氯甲烷 为溶剂， 生成 [PdCl2(1,1'-bis(diethylphosphino)ferrocene)]
  参考文献：
  名称：

  Ethylene Carbonylation in Methanol and in Aqueous Media by Palladium(II) Catalysts Modified with 1,1‘-Bis(dialkylphosphino)ferrocenes

  摘要：

  Palladium(II) complexes with the formula [Pd(H2O)(OTs)(P-P)]OTs, where P-P is 1,1'-bis-(dimethylphosphino)ferrocene (dmpf), 1,1'-bis(diethylphosphino)ferrocene (depf), or 1,1'-bis-(diisopropylphosphino)ferrocene (dippf), have been synthesized and used to catalyze the carbonylation of ethylene in MeOH, water, or a 1/1 water/1,4-dioxane mixture. In MeOH, the reactions catalyzed by the dmpf and depf complexes gave alternating polyketone (alt-E-CO), while methyl propanoate and 3-pentanone were selectively produced with the dippf catalyst. The last catalyst was inactive in aqueous solvent. In contrast, the dmpf and depf catalysts were active in either water or water/1,4-dioxane for the copolymerization of CO with ethylene. These two catalysts were efficient also for the terpolymerization of CO with ethylene and propene in MeOH or water/1,4-dioxane. Operando high-pressure NMR experiments and in situ reactions with model compounds have provided useful information to rationalize the activity and selectivity of the catalytic systems investigated.

  DOI：

  10.1021/om049109w
• 作为产物：
  描述：

  二茂铁 、 氯化二乙基磷 在 n-BuLi 、 N,N,N',N'-tetramethylethylenediamine 作用下， 以 正己烷 为溶剂， 以67%的产率得到1,1'-bis(diethylphosphino)ferrocene
  参考文献：
  名称：

  Synthesis and Reactivity of Tungsten− and Molybdenum−Dinitrogen Complexes Bearing Ferrocenyldiphosphines toward Protonolysis

  摘要：

  Novel tungsten- and molybdenum -dinitrogen complexes bearing 1,1'-bis(diethylphosphino)ferrocenes as auxiliary ligands have been prepared and characterized crystallographically. Reactions of these complexes with an excess amount of sulfuric acid in methanol at room temperature yield ammonia in good yields. This result is in sharp contrast to the previous result that protonolysis of tungsten- and molybdenum -dinitrogen complexes bearing conventional diphosphines such as 1,2-bis(diphenylphosphino)ethane does not produce ammonia. Reactions of the dinitrogen complexes with 2 equiv of trifluoromethanesulfonic acid give the corresponding hydrazido complexes as intermediates. Molecular structures of these hydrazido complexes have been determined by X-ray analysis.

  DOI：

  10.1021/om800327j

文献信息

• Propargylic Substitution Reaction Catalyzed by Group IV (Ti, Zr, Hf)–Ru Heterobimetallic Complexes
  作者：Takamasa Miyazaki、Yoshiaki Tanabe、Masahiro Yuki、Yoshihiro Miyake、Yoshiaki Nishibayashi

  DOI：10.1021/om200292p

  日期：2011.6.13

  A series of heterobimetallic complexes consisting of group IV metallocenyl diphosphines and Ru were synthesized and structurally characterized. Most of them work as catalysts toward propargylic substitution reaction of 1,1-diphenyl-2-propyn-1-ol (4) with EtOH. The stoichiometric reactions of the heterobimetallic complexes [MCl2(μ-η5:η1-C5H4PEt2)2RuClCp*] (M = Zr, Hf) with 4 and NaBArF4 afforded key

  合成了一系列由IV族金属茂基二膦和Ru组成的杂双金属配合物，并对其结构进行了表征。它们中的大多数用作催化1，1-二苯基-2-丙炔-1-醇（4）与EtOH的炔丙基取代反应的催化剂。双核配合物的化学计量反应[的MC1 2（μ-η 5：η 1 -C 5 ħ 4 PET 2）2 RuClCP *]（M =锆，铪）与4和NaBARhref=https://www.molaid.com/MS_77868 target="_blank">BAr ˚F 4种得到密钥反应中间体allenylidene配合物[的MC1 2（μ-η 5：η 1 -C 5 ħ4 PET 2）2 RuCP *（═C═C═CPh 2）] BAR ˚F 4，其分子结构通过X-射线分析证实。提出了一种可行的催化反应途径，其中Ⅳ族金属氯化物和Ru部分协同作用。
• Design and Preparation of Molybdenum-Dinitrogen Complexes with Ferrocenyldiphosphine and Pentamethylcyclopentadienyl Moieties as Auxiliary Ligands
  作者：Takamasa Miyazaki、Yoshiaki Tanabe、Masahiro Yuki、Yoshihiro Miyake、Kazunari Nakajima、Yoshiaki Nishibayashi

  DOI：10.1002/chem.201302700

  日期：2013.9.2

  Fix me! Molybdenum–dinitrogen complexes containing ferrocenyldiphosphine and pentamethylcyclopentadienyl moieties as auxiliary ligands have been designed, prepared, and characterized (see scheme). The ferrocenyldiphosphine works as a unique ligand to inhibit dissociation of dinitrogen, as well as to make the coordinated molecular dinitrogen reactive toward electrophiles.

  整我！已经设计，制备和表征了含有二茂铁基二膦和五甲基环戊二烯基部分作为辅助配体的钼-二氮配合物。二茂铁基二膦用作独特的配体，以抑制二氮的离解，并使配位的分子二氮对亲电子试剂具有反应性。
• Ambi-Valence Taken Literally: Ruthenium vs Iron Oxidation in (1,1′-Diphosphinoferrocene)ruthenium(II) Hydride and Chloride Complexes as Deduced from Spectroelectrochemistry of the Heterodimetallic “Mixed-Valent” Intermediates
  作者：Torsten Sixt、Monika Sieger、Michael J. Krafft、Denis Bubrin、Jan Fiedler、Wolfgang Kaim

  DOI：10.1021/om1004258

  日期：2010.11.8

  diphosphinoferrocenes (dpf) 1,1′-bis(diphenylphosphino)ferrocene (dppf; complex 3), 1,1′-bis(diisopropylphosphino)ferrocene (dippf; complex 4), and 1,1′-bis(diethylphosphino)ferrocene (depf; complex 5) as well as the structurally characterized hydride complex [(C5Me5)RuH(dippf)] (2). In contrast to the case for 2, with an approximately staggered ferrocene conformation, the chloride complexes 3−5 exhibit a syn-periplanar

  结合两个不同的氧化还原活性有机金属部分，我们制备了化合物[（Cym）RuCl（dpf）]（PF 6），其中Cym = p -cymene = 1-异丙基-4-甲基苯，和二膦基二茂铁（dpf）1， 1'-双（二苯基膦基）二茂铁（DPPF;配合物3），1,1'-双（二异丙基膦基）二茂铁（dippf;配合物4）和1,1'-双（二乙基膦基）二茂铁（depf;配合物5）以及结构表征的氢化物配合物[（C 5 Me 5）RuH（dippf）]（2）。与此相反的情况下为2，以大致交错的二茂铁的构象中，所述氯化物络合物3 - 5由于在固体和溶液中存在Cl···H（C 5 H 4）相互作用，因此具有顺周二茂铁排列。相关的新化合物〔（CYM）期RuH（DPPF）]（PF 6）（6）和三核（μ-DPF）[（CYM）的RuCl 2）] 2（7 - 9）也获得和通过鉴定1 H和31 P NMR光谱。2 − 6和已知的[（C
• Iron(II) versus osmium(II) oxidation in 1,1′-bis(diorganophosphino)ferrocene–osmium(II) complexes
  作者：Wolfgang Kaim、Torsten Sixt、Michael Weber、Jan Fiedler

  DOI：10.1016/s0022-328x(01)00898-1

  日期：2001.12

  The compounds [(Cym)OsCl(dxpf)](PF6), Cym = p-cymene and dxpf: 1,1'-bis(diphenylphosphino)ferrocene (dppf), 1, 1'-bis(diethylphosphino)ferrocene (depf) or 1,1'-bis(diisopropylphosphino)ferrocene (dippf), were synthesized and characterized by NMR (H-1, P-31) and, in the case of [(Cym)OsCl(dppf](PF6), by X-ray structure analysis of the acetonitrile solvate. EPR and UV-vis spectroelectrochemistry indicate the formation of an osmium(II)-ferrocenium species on reversible one-electron oxidation. The second oxidation and the reduction are electrochemically irreversible. (C) 2001 Elsevier Science B.V. All rights reserved.