1,1',2'-tris(diphenylphosphino)-4-tert-butylferrocene | 878190-65-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,1',2'-tris(diphenylphosphino)-4-tert-butylferrocene
• 英文别名: 1,1',2-tris(diphenylphosphino)-4-tert-butylferrocene；(3-Tert-butyl-5-diphenylphosphanylcyclopenta-1,4-dien-1-yl)-diphenylphosphane;cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;iron(2+)；(3-tert-butyl-5-diphenylphosphanylcyclopenta-1,4-dien-1-yl)-diphenylphosphane;cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;iron(2+)
• CAS: 878190-65-9
• 化学式: C₅₀H₄₅FeP₃
• 分子量: 794.676
• InChiKey: ZSSQLVWBGOZSBK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.38
• 重原子数：
  54
• 可旋转键数：
  10
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.08
• 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：

  氯化镍二甲氧基乙烷 、 1,1',2'-tris(diphenylphosphino)-4-tert-butylferrocene 以 乙腈 为溶剂， 以73%的产率得到[NiCl2(1,1',2-tris(diphenylphosphino)-4-tert-butylferrocene)]
  参考文献：
  名称：

  Coordination Chemistry of Tetra- and Tridentate Ferrocenyl Polyphosphines: An Unprecedented [1,1′-Heteroannular and 2,3-Homoannular]-Phosphorus-Bonding Framework in a Metallocene Dinuclear Coordination Complex

  摘要：

  Palladium(II) and nickel(II) halide complexes of the ferrocenyl polyphosphines 1,1',2,3-tetrakis(diphenylphosphino)ferrocene (1), and 1,1',2-tris(diphenylphosphino)-4-tert-butylferrocene (5) were prepared and characterized by multinuclear NMR. The metallo-ligand 1, the palladium [Pd2Cl4(1)] (3b) and nickel [NiCl2(5)] (6) coordination complexes were additionally characterized by X-ray diffraction crystallography. The behavior of 1 toward coordination to nickel and palladium was surprisingly different because the coordination of a second metal center after the initial 1,2-phosphorus-bonding of nickel was markedly difficult. The preference of nickel for 1,2-P coordination on 1,1'-bonding was confirmed by the exclusive formation of 6 from 5. The changes noted between the solid state structure of the ligand 1 and the structure obtained for the dinuclear palladium complex 3b reveal the rotational flexibility of this tetraphosphine. This flexibility is at the origin of the unique framework for a metallocenic dinuclear metal complex in which both coexist a 1,1'-heteroannular chelating P-bonding and a 2,3-homoannular chelating P-bonding with two palladium centers. Some reported specimens of ferrocenyl polyphosphines of constrained geometry have previously revealed that phosphorus lone pair overlap can lead to very intense "through-space" (PP)-P-31-P-31 nuclear spin-spin coupling constants (J(PP)) (J. Am. Chem. Soc. 2004, 126 (35), 11077-11087] in solution phase, In these cases, an internuclear distance between heteroannular phosphorus atoms below 4.9 angstrom, with an adequate orientation of the lone-pairs in the solid state and in solution, was a necessary parameter. The flexibility of the new polyphosphines 1 and 5 does not allow that spatial proximity (internuclear distances between heteroannular phosphorus above 5.2 angstrom in the solid state); accordingly the expected through-space nuclear spin-spin coupling constants were not detected in any of their coordination complexes nor in 1.

  DOI：

  10.1021/ic7022105
• 作为产物：
  描述：

  iron(II) chloride 、 lithium diphenylphosphinocyclopentadienyl 、 1,2-bis(diphenylphosphino)-4-tert-butylcyclopentadienyl lithium 以 四氢呋喃 为溶剂， 以84%的产率得到1,1',2'-tris(diphenylphosphino)-4-tert-butylferrocene
  参考文献：
  名称：

  Coordination Chemistry of Tetra- and Tridentate Ferrocenyl Polyphosphines: An Unprecedented [1,1′-Heteroannular and 2,3-Homoannular]-Phosphorus-Bonding Framework in a Metallocene Dinuclear Coordination Complex

  摘要：

  Palladium(II) and nickel(II) halide complexes of the ferrocenyl polyphosphines 1,1',2,3-tetrakis(diphenylphosphino)ferrocene (1), and 1,1',2-tris(diphenylphosphino)-4-tert-butylferrocene (5) were prepared and characterized by multinuclear NMR. The metallo-ligand 1, the palladium [Pd2Cl4(1)] (3b) and nickel [NiCl2(5)] (6) coordination complexes were additionally characterized by X-ray diffraction crystallography. The behavior of 1 toward coordination to nickel and palladium was surprisingly different because the coordination of a second metal center after the initial 1,2-phosphorus-bonding of nickel was markedly difficult. The preference of nickel for 1,2-P coordination on 1,1'-bonding was confirmed by the exclusive formation of 6 from 5. The changes noted between the solid state structure of the ligand 1 and the structure obtained for the dinuclear palladium complex 3b reveal the rotational flexibility of this tetraphosphine. This flexibility is at the origin of the unique framework for a metallocenic dinuclear metal complex in which both coexist a 1,1'-heteroannular chelating P-bonding and a 2,3-homoannular chelating P-bonding with two palladium centers. Some reported specimens of ferrocenyl polyphosphines of constrained geometry have previously revealed that phosphorus lone pair overlap can lead to very intense "through-space" (PP)-P-31-P-31 nuclear spin-spin coupling constants (J(PP)) (J. Am. Chem. Soc. 2004, 126 (35), 11077-11087] in solution phase, In these cases, an internuclear distance between heteroannular phosphorus atoms below 4.9 angstrom, with an adequate orientation of the lone-pairs in the solid state and in solution, was a necessary parameter. The flexibility of the new polyphosphines 1 and 5 does not allow that spatial proximity (internuclear distances between heteroannular phosphorus above 5.2 angstrom in the solid state); accordingly the expected through-space nuclear spin-spin coupling constants were not detected in any of their coordination complexes nor in 1.

  DOI：

  10.1021/ic7022105
• 作为试剂：
  描述：

  苯胺 、 1,2-二溴苯 在 bis(η3-allyl-μ-chloropalladium(II)) 、 1,1',2'-tris(diphenylphosphino)-4-tert-butylferrocene 、 potassium tert-butylate 作用下， 以 甲苯 为溶剂， 反应 18.0h， 以30%的产率得到(2-溴苯基)苯胺
  参考文献：
  名称：

  钯催化芳基二卤化物与空气稳定的二茂铁二茂铁三和二膦形成仲胺和叔胺：[PdCl 2（DPPF）]以外的有效催化剂的合成和X射线结构

  摘要：

  健壮，空气稳定的三齿和二齿ferrocenylphosphines 1,2-双（二苯基膦基）-1' - （二异丙异丙膦基）-4-叔-butylferrocene，L5，和1,1'-双（二异异丙膦基）-3,3- 3'-双（叔丁基）二茂铁，L9，用1摩尔％[的PdCl（η的组合3 -C 3 H ^ 5）] 2导致了两个新的催化体系，其允许苯胺衍生物的耦合与单和dihaloarenes形成官能化的二芳基胺和三芳基胺。反应极好的选择性避免了底物和产物的有害脱卤作用。相关配合物[PdCl 2的X射线结构表征（L9）]报道，其中配体L9在其内消旋形式显著失真。

  DOI：

  10.1016/j.catcom.2014.03.012

文献信息

• General Route to Dissymmetric Heteroannular-Functionalized Ferrocenyl 1,2-Diphosphines:  Selective Synthesis and Characterization of a New Class of Tri- and Tetrasubstituted Ferrocenyl Compounds
  作者：V. V. Ivanov、J.-C. Hierso、R. Amardeil、P. Meunier

  DOI：10.1021/om050882g

  日期：2006.2.1

  Several monosubstituted-cyclopentadienyl anions (A-Li) and [1,2-bis(diphenylphosphino)-4-tert-butylcyclopentadienyl]lithium (B-Li) react with FeCl2 to afford a novel class of multidentate ferrocenylphosphines (A-Fe-B). The proposed synthetic method represents a unique means to produce achiral dissymmetric 1,1‘,2-substituted ferrocenes (A-Fe-B) bearing a heteroannular 1‘-substituent which is different

  几个单取代的环戊二烯基阴离子（A- Li）和[1,2-双（二苯基膦基）-4-叔丁基环戊二烯基]锂（B - Li）与FeCl 2反应，得到一类新型的多齿二茂铁基膦（A -Fe- B）。拟议的合成方法代表了一种独特的方法，可生产非均相的1,1'，2-取代的二茂铁（A -Fe- B），其带有不同于同环1和2取代基的异环1'-取代基。两步反应的选择性有利于形成所需的不对称产物（A -Fe- B），而不是同时形成对称的二取代和四取代的二茂铁（A -Fe- A和B -Fe- B）。因此，该方法允许访问大量不对称的多齿金属配体，尤其是当人们认为功能化的Cp盐在数量和多样性方面不断扩展时。在此，重点放在金属配体的1 H，13 C和31 P NMR表征上。有几个例子显示出有趣的构象特性和罕见的“贯穿空间”磷核自旋耦合。
• Coordination Chemistry of Tetra- and Tridentate Ferrocenyl Polyphosphines: An Unprecedented [1,1′-Heteroannular and 2,3-Homoannular]-Phosphorus-Bonding Framework in a Metallocene Dinuclear Coordination Complex
  作者：D. A. Thomas、V. V. Ivanov、I. R. Butler、P. N. Horton、P. Meunier、J.-C. Hierso

  DOI：10.1021/ic7022105

  日期：2008.3.1

  Palladium(II) and nickel(II) halide complexes of the ferrocenyl polyphosphines 1,1',2,3-tetrakis(diphenylphosphino)ferrocene (1), and 1,1',2-tris(diphenylphosphino)-4-tert-butylferrocene (5) were prepared and characterized by multinuclear NMR. The metallo-ligand 1, the palladium [Pd2Cl4(1)] (3b) and nickel [NiCl2(5)] (6) coordination complexes were additionally characterized by X-ray diffraction crystallography. The behavior of 1 toward coordination to nickel and palladium was surprisingly different because the coordination of a second metal center after the initial 1,2-phosphorus-bonding of nickel was markedly difficult. The preference of nickel for 1,2-P coordination on 1,1'-bonding was confirmed by the exclusive formation of 6 from 5. The changes noted between the solid state structure of the ligand 1 and the structure obtained for the dinuclear palladium complex 3b reveal the rotational flexibility of this tetraphosphine. This flexibility is at the origin of the unique framework for a metallocenic dinuclear metal complex in which both coexist a 1,1'-heteroannular chelating P-bonding and a 2,3-homoannular chelating P-bonding with two palladium centers. Some reported specimens of ferrocenyl polyphosphines of constrained geometry have previously revealed that phosphorus lone pair overlap can lead to very intense "through-space" (PP)-P-31-P-31 nuclear spin-spin coupling constants (J(PP)) (J. Am. Chem. Soc. 2004, 126 (35), 11077-11087] in solution phase, In these cases, an internuclear distance between heteroannular phosphorus atoms below 4.9 angstrom, with an adequate orientation of the lone-pairs in the solid state and in solution, was a necessary parameter. The flexibility of the new polyphosphines 1 and 5 does not allow that spatial proximity (internuclear distances between heteroannular phosphorus above 5.2 angstrom in the solid state); accordingly the expected through-space nuclear spin-spin coupling constants were not detected in any of their coordination complexes nor in 1.