exo,exo,syn-1,12-dichloro-1,12-diphospha[1.1]ferrocenophane | 877843-68-0

• 分子结构分类: 有机化合物
• 英文名称: exo,exo,syn-1,12-dichloro-1,12-diphospha[1.1]ferrocenophane
• 英文别名: chloro-di(cyclopenta-1,3-dien-1-yl)phosphane;iron(2+)
• CAS: 877843-68-0
• 化学式: C₂₀H₁₆Cl₂Fe₂P₂
• 分子量: 500.895
• InChiKey: GIGHDUPBQVKDQS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  trimethylsilylmethyllithium 、 exo,exo,syn-1,12-dichloro-1,12-diphospha[1.1]ferrocenophane 以 四氢呋喃 、 正戊烷 为溶剂， 以55%的产率得到di(cyclopenta-1,3-dien-1-yl)-(trimethylsilylmethyl)phosphane;iron(2+)
  参考文献：
  名称：

  磷桥[1.1]二茂铁烷的立体选择性合成和配位行为

  摘要：

  用氯化的混合物的盐酸顺-和反-P（NET 2）-bridged [1.1]二茂铁基3衍生自的[Fe {（η 5 -C 5 H ^ 4）的PCl（NET 2）} 2 ] 2伴随着容易防-到-顺式转换，得到顺式的的PCl桥接异构体[1.1]二茂铁基顺式- 4收率选择性在90％以上，和治疗的顺式- 4与PhLi中，Me 3 SICH 2 Li或p-TolMgBr提供相应的二芳基或二烷基化化合物syn - 5至syn - 7。的反应顺- 5与[的PdCl 2（COD）]，[PDME 2（TMEDA）]，和的NiCl 2分别给出四坐标[的PdCl 2（顺式- 5）]，[PDME 2（顺式- 5）]，和[NiCl 2（syn - 5）]配合物，前两种具有扭曲的正方形平面结构，后者采用四面体几何形状。此外，syn - 5充当钢琴凳上的Mn羰基配合物片段的桥连配体，从而产生新型双核配合物[{Cp'Mn（CO）2

  DOI：

  10.1021/om050809q
• 作为产物：
  描述：

  盐酸 、 exo,exo,anti-1,12-bis(diethylamino)-1,12-diphospha[1.1]ferrocenophane 以 乙醚 为溶剂， 以90%的产率得到exo,exo,syn-1,12-dichloro-1,12-diphospha[1.1]ferrocenophane
  参考文献：
  名称：

  磷桥[1.1]二茂铁烷的立体选择性合成和配位行为

  摘要：

  用氯化的混合物的盐酸顺-和反-P（NET 2）-bridged [1.1]二茂铁基3衍生自的[Fe {（η 5 -C 5 H ^ 4）的PCl（NET 2）} 2 ] 2伴随着容易防-到-顺式转换，得到顺式的的PCl桥接异构体[1.1]二茂铁基顺式- 4收率选择性在90％以上，和治疗的顺式- 4与PhLi中，Me 3 SICH 2 Li或p-TolMgBr提供相应的二芳基或二烷基化化合物syn - 5至syn - 7。的反应顺- 5与[的PdCl 2（COD）]，[PDME 2（TMEDA）]，和的NiCl 2分别给出四坐标[的PdCl 2（顺式- 5）]，[PDME 2（顺式- 5）]，和[NiCl 2（syn - 5）]配合物，前两种具有扭曲的正方形平面结构，后者采用四面体几何形状。此外，syn - 5充当钢琴凳上的Mn羰基配合物片段的桥连配体，从而产生新型双核配合物[{Cp'Mn（CO）2

  DOI：

  10.1021/om050809q

文献信息

• Synthesis of Binuclear Complexes Bound in an Enlarged Tetraphosphamacrocycle: Two Diphosphine Metal Units Linked in Front-to-Front Style
  作者：Tsutomu Mizuta、Yuta Inami、Kazuyuki Kubo、Katsuhiko Miyoshi

  DOI：10.1021/ic9013224

  日期：2009.8.17

  A large-hole tetraphosphamacrocycle 2, with four phosphorus centers separated at the corners of a 3.7 angstrom wide and 9.7 angstrom long rectangle, was synthesized by a stepwise cyclization reaction between PCI-bridged [1.1]ferrocenophane and bisphenol A in a 2:2 ratio. The macrocycle 2 could incorporate two Ag+ or Pt-0 fragments in the hole to provide binuclear complexes, which were identified as mu-2-[Ag(NCMe)(2)](2)(BF4)(2) (3) and mu-2-[Pt(PhCCPh)](2) (5), respectively, using X-ray and spectroscopic analysis. The X-ray structure of 3 demonstrates that the macrocycle 2 serves as a framework in which two diphosphine silver units are aligned in a front-to-front style, while that of 5 indicates that 2 can also bind two bulky Pt(PhCCPh) fragments by the flexible change of its conformation.
• Hydrolysis of Me3SiCH2 groups on a double-chelating bis(ferrocenediyl)diphosphine coordinating to a Pt(0) center
  作者：Kanako Abe、Kazuyuki Kubo、Shoko Kume、Tsutomu Mizuta

  DOI：10.1016/j.poly.2016.02.027

  日期：2016.5

  The double-chelating diphosphine ligand PCH2SiMe3-bridged [1.1]ferrocenophane (1), in which two phosphorus donor atoms are doubly linked with two ferrocene groups and with a Me3SiCH2 group on each phosphorus center, was reacted with [Pt(PPh3)(3)] to form the tricoordinated Pt(0) complex [Pt(1) (PPh3)]. Refluxing of this complex with another equivalent of 1 in THF inadvertently containing traces of water was found to successively hydrolyze the four Me3SiCH2 groups of [Pt(1)(2)] to eventually form [Pt(2)(2)], in which all the initial Me3Si groups of [Pt(1)(2)] were replaced with hydrogens. The molecular structure of [Pt(2)(2)], as determined by X-ray analysis, shows stereochemical congestion between the two ligands. Since hydrolysis in refluxing THF did not proceed at all for both the free ligand 1 and the Pt(II) complex [PtCl2(1)], the stereochemical congestion of the Pt(0) complexes having two double-chelating diphosphine ligands is probably responsible for the observed hydrolysis. (C) 2016 Elsevier Ltd. All rights reserved.