1,1'-dibromo-2,2'-bis(diphenylphosphino)ferrocene | 259660-17-8

• 英文名称: 1,1'-dibromo-2,2'-bis(diphenylphosphino)ferrocene
• CAS: 259660-17-8
• 化学式: C₃₄H₂₆Br₂FeP₂
• 分子量: 712.183
• InChiKey: JOHZIHSCJBDTGG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  1,1'-dibromoferrocene 、 二苯基氯化膦 在 lithium diisopropylamide 作用下， 以 四氢呋喃 为溶剂， 生成 溴代二茂铁 、 1,1'-dibromo-2,5-bis(diphenylphosphino)ferrocene 、 1,1'-dibromo-2,2'-bis(diphenylphosphino)ferrocene
  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