1,1'-bis(2,4,6-tris[bis(trimethylsilyl)methyl]phenyldiphosphenyl)ferrocene | 882693-32-5

• 英文名称: 1,1'-bis(2,4,6-tris[bis(trimethylsilyl)methyl]phenyldiphosphenyl)ferrocene
• CAS: 882693-32-5
• 化学式: C₆₄H₁₂₆FeP₄Si₁₂
• 分子量: 1412.47
• InChiKey: AQHAIYYGFNLZRO-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：

  1,1'-bis(2,4,6-tris[bis(trimethylsilyl)methyl]phenyldiphosphenyl)ferrocene 以 甲苯 为溶剂， 以46%的产率得到
  参考文献：
  名称：

  富磷二茂铁

  摘要：

  图形摘要 摘要 一些新型的富磷 [3] 二茂铁被报道为具有 PPP 或 NPN 桥。通过分子内热 2+2 加成从相应的二膦获得 P-桥连二茂铁。还探索了二膦对氢氯化的反应性。NPN 二茂铁是通过盐复分解获得的，是此类化合物的罕见例子之一。除了光谱表征外，其结构还通过 X 射线晶体学进行了阐明。

  DOI：

  10.1080/10426507.2014.984025
• 作为产物：
  描述：

  bis-1,3-dihydrotriphosphane 以 not given 为溶剂， 生成 1,1'-bis(2,4,6-tris[bis(trimethylsilyl)methyl]phenyldiphosphenyl)ferrocene
  参考文献：
  名称：

  Synthesis of 1,1‘-Ferrocenylene-Bridged Bisdiphosphenes

  摘要：

  A simple synthetic access to the first ferrocenylene-bridged bisdiphosphenes Fe(C5H4-P=P-R)(2) is reported. The unsaturated P=P units require steric protection by adjacent substituents such as Dmp (2.6-dimesitylphenyl) and Tbt (2.4,6-tris[bis(trimethylsilyl)methyl]phenyl) and should be capable of conjugative interaction with the central metallocene unit. The electronic situation in these molecules has been assessed on the basis of DFT calculations. As a derivative of the Tbt-substituted bisdiphosphene with Tbt-PH2, the resulting ferrocenylene-bridged bis-1,3-dihydrotriphosphane has been characterized by X-ray crystallography.

  DOI：

  10.1021/om060073c

文献信息

• Kinetically Stabilized 1,1′-Bis[(<i>E</i>)-diphosphenyl]ferrocenes: Syntheses, Structures, Properties, and Reactivity
  作者：Noriyoshi Nagahora、Takahiro Sasamori、Yasuaki Watanabe、Yukio Furukawa、Norihiro Tokitoh

  DOI：10.1246/bcsj.80.1884

  日期：2007.10.15

  Kinetically stabilized 1,1′-bis[(E)-diphosphenyl]ferrocenes were synthesized by taking advantage of extremely bulky substituents, 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (denoted as Tbt) and 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl (denoted as Bbt) groups, and characterized by the spectroscopic and X-ray crystallographic analyses. The electronic structures of the 1,1′-bis[(E)-diphosphenyl]ferrocenes were determined by analyzing electronic spectra, the transitions of which were reasonably assigned based on theoretical calculations. In the cyclic voltammograms, there were two well-defined reversible one-electron reduction couples corresponding to the intramolecular two diphosphene units. Furthermore, the 1,1′-bis[(E)-diphosphenyl]ferrocene was found to undergo ligand-exchange reactions with group 6 metal carbonyl complexes along with the E-to-Z isomerization of the diphosphene moieties, leading to the formation of the corresponding 1,1′-bis[(Z)-diphosphenyl]ferrocene group 6 metal tetracarbonyl complexes, [M(CO)4(Z,Z)-(BbtP=PC5H4)2Fe}] (M=Cr, Mo, and W). The molecular structures of these complexes were determined by spectroscopic analyses (1H, 13C, and 31P NMR spectra, and UV–vis spectra), and that of the tungsten complex was determined by X-ray crystallographic analysis. Several types of d→π∗P=P electron transitions due to the iron and group 6 metals were detected by using UV–vis spectroscopy, and these results were supported by theoretical calculations.

  通过利用极 bulky 取代基 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl（简称 Tbt）和 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl（简称 Bbt）合成了动力学稳定的 1,1′-双[(E)-二膦基]铁烯，并通过光谱学和 X 射线晶体学分析进行了表征。通过分析电子光谱确定了 1,1′-双[(E)-二膦基]铁烯的电子结构，过渡的合理归属基于理论计算。在循环伏安图中，观察到与分子内两个二膦单位对应的两个明确的可逆一电子还原对。此外，发现 1,1′-双[(E)-二膦基]铁烯与 6 族金属碳氧络合物发生配体交换反应，同时导致二膦基团的 E-Z 异构化，形成相应的 1,1′-双[(Z)-二膦基]铁烯 6 族金属四羧基络合物 [M(CO)4(Z,Z)-(BbtP=PC5H4)2Fe}]（M=Cr、Mo 和 W）。这些络合物的分子结构通过光谱分析（1H、13C 和 31P NMR 光谱，以及 UV–vis 光谱）确定，其中钨络合物的结构则通过 X 射线晶体学分析确定。使用 UV–vis 光谱检测到了由于铁和 6 族金属引起的几种类型的 d→π∗ P=P 电子跃迁，且这些结果得到了理论计算的支持。
• Syntheses, Structures, and Properties of the First Stable 1,1′-Bis(diphosphenyl)ferrocenes
  作者：Noriyoshi Nagahora、Takahiro Sasamori、Norihiro Tokitoh

  DOI：10.1246/cl.2006.220

  日期：2006.2

  Kinetically stabilized 1,1′-bis(diphosphenyl)ferrocenes have been synthesized by taking advantage of extremely bulky substituents, 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (Tbt) and 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl (Bbt) groups, and fully characterized by the spectroscopic and X-ray crystallographic analyses. The electrochemical behavior showed well-defined two reversible one-electron reduction couples.

  利用 2,4,6- 三[双（三甲基硅基）甲基]苯基（Tbt）和 2,6- 双[双（三甲基硅基）甲基]-4-[三（三甲基硅基）甲基]苯基（Bbt）这两个极其笨重的取代基，合成了动力学稳定的 1,1′-双（二磷苯基）二茂铁，并通过光谱和 X 射线晶体学分析对其进行了全面表征。电化学行为显示出定义明确的两个可逆的单电子还原偶。