(η5-C5H5)Fe(CO)(pyridine)(SiEt3) | 1061599-58-3

• 英文名称: (η5-C5H5)Fe(CO)(pyridine)(SiEt3)
• 英文别名: (η⁵-C₅H₅)Fe(CO)(pyridine)(SiEt₃)；CpFe(CO)(py)(SiEt₃)；[iron(II)(η5-C5H5)(CO)(pyridine)(SiEt3)]；[Cp(iron)(CO)(triethylsilyl)(pyridine)]；(C5H5)Fe(CO)(pyridine)(SiEt3)；(C5H5)Fe(CO)(py)(SiEt3)
• CAS: 1061599-58-3
• 化学式: C₁₇H₂₅FeNOSi
• 分子量: 343.324
• InChiKey: RDKRVIHQJCBDGU-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：

  乙醇 、 (η5-C5H5)Fe(CO)(pyridine)(SiEt3) 以 甲苯 为溶剂， 反应 24.0h， 以21%的产率得到乙氧基三乙基硅烷
  参考文献：
  名称：

  Dehydrogenative coupling of alcohol with hydrosilane catalyzed by an iron complex

  摘要：

  Silane alcoholysis of triethylsilane (Et3SiH) with alcohol (ROH) with the help of CpFe(CO)(2)Me (1) has been achieved to produce triethylsilyl ether (ROSiEt3) under the thermal condition. For some alcohols, the iron complex served as a catalyst. A 16e silyl iron complex (CpFe(CO)(SiEt3)) was proposed to be one of active iron species. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2015.02.019

文献信息

• Dehydrogenative desulfurization of thiourea derivatives to give carbodiimides, using hydrosilane and an iron complex
  作者：Kazumasa Hayasaka、Kozo Fukumoto、Hiroshi Nakazawa

  DOI：10.1039/c3dt50996f

  日期：——

  Dehydrogenative desulfurization of thiourea derivatives (RNHC(S)NHR′) has been achieved, to give carbodiimides (RNCNR′), in the reaction with hydrosilane and (η5-C5H5)Fe(CO)2Me. The obtained carbodiimide reacted with (η5-C5H5)Fe(CO)(SiR3) formed in the reaction to give an N-silylated η2-amidino iron complex, which was isolated and then characterized by X-ray analysis.

  通过用氢硅烷和(η5-C5H5)Fe(CO)2Me反应，实现了硫脲衍生物(RNHC(S)NHR′)的脱氢脱硫反应，生成了二亚胺(RNCNR′)。所得到的二亚胺与反应中形成的(η5- )Fe(CO)(SiR3)反应，得到了一个N-硅基化的η2-胺基铁配合物，该配合物被分离并通过X射线分析进行了表征。
• Si–CN Bond Cleavage of Silyl Cyanides by an Iron Catalyst. A New Route of Silyl Cyanide Formation
  作者：Andrea Renzetti、Nobuaki Koga、Hiroshi Nakazawa

  DOI：10.1246/bcsj.20130206

  日期：2014.1.15

  The reaction of silyl cyanide (R3SiCN) with hydrosilane (R′3SiH) in the presence of a catalytic amount of [(η5-C5H5)Fe(CO)2Me] formed R′3SiCN and R3SiH. This reaction involves Si–CN bond cleavage and provides a new method for the preparation of silyl cyanides. DFT calculation showed that coordinatively unsaturated [(η5-C5H5)Fe(CO)(SiMe3)] reacts exothermically with Me3SiCN to give the CN π-coordinated complex, [(η5-C5H5)Fe(CO)(η2-Me3SiCN)(SiMe3)], followed by exothermic silyl migration from the iron to the nitrogen atom of the η2-coordinated Me3SiCN with the activation energy of 8.8 kcal mol−1 to give [(η5-C5H5)Fe(CO)(Me3SiC=NSiMe3-κC,κN)]. The complex is one of the intermediates in the catalytic cycle. The related complex [(η5-C5Me5)Fe(CO)(κ-C,N-t-BuMe2SiC=NSiPh3)] was isolated in the reaction of [(η5-C5Me5)Fe(CO)(py)(SiPh3)] with t-BuMe2SiCN and characterized by 1H, 13C, and 29Si NMR spectroscopy. The activation energy of the Si–CN bond cleavage in [(η5-C5H5)Fe(CO)(κ-C,N-Me3SiC=NSiMe3)] was evaluated by DFT calculation to be 33.7 kcal mol−1 which is comparable to that in the reaction of acetonitrile (32.9 kcal mol−1).

  叔丁基氰化硅（R3SiCN）与氢硅烷（R′3SiH）在催化量的[(η5-C5H5)Fe(CO)2Me]存在下反应形成了R′3SiCN和R3SiH。该反应涉及Si–CN键的断裂，并提供了一种制备氰化硅的新方法。DFT计算表明，配位不饱和的[(η5- )Fe(CO)(SiMe3)]与Me3SiCN发生放热反应，生成CN π-配位复合物[(η5- )Fe(CO)(η2-Me3SiCN)(SiMe3)]，随后发生铁原子向η2-配位Me3SiCN的氮原子的放热硅迁移，活化能为8.8 kcal mol−1，生成[(η5- )Fe(CO)(Me3SiC=NSiMe3-κC,κN)]。该复合物是催化循环中的一个中间体。在[(η5-C5Me5)Fe(CO)(py)(SiPh3)]与t-BuMe2SiCN反应中，相关的复合物[(η5-C5Me5)Fe(CO)(κ-C,N-t-BuMe2SiC=NSiPh3)]被分离并通过1H、13C和29Si NMR光谱进行了表征。在[(η5- )Fe(CO)(κ-C,N-Me3SiC=NSiMe3)]中Si–CN键断裂的活化能通过DFT计算评估为33.7 kcal mol−1，且与乙腈反应中的活化能（32.9 kcal mol−1）相当。
• Desulfurization of N,N-dimethylthioformamide by hydrosilane with the help of an iron complex. Isolation and characterization of an iron–carbene complex as an intermediate of CS double bond cleavage
  作者：Kozo Fukumoto、Akane Sakai、Tsukuru Oya、Hiroshi Nakazawa

  DOI：10.1039/c2cc17163e

  日期：——

  (Me(2)NCHS) by hydrosilane has been achieved under photo irradiation in the presence of a methyl iron complex. The reaction sequences have been proposed, in which silyl migration from Fe to S of thioformamide triggers the cleavage of a C=S bond to give a carbene-iron complex. This intermediate was isolated and characterized by X-ray analysis.

  N，N-二甲基硫代甲酰胺（Me（2）NCHS）在甲基铁络合物的存在下在光照射下已通过氢化硅烷实现脱硫。已经提出了反应序列，其中甲硅烷基从Fe到硫代甲酰胺的S的迁移触发了C ＝ S键的裂解，从而得到卡宾-铁络合物。分离出该中间体，并通过X射线分析对其进行表征。
• Itazaki, Masumi; Ueda, Kensuke; Nakazawa, Hiroshi, Angewandte Chemie - International Edition, 2009, vol. 48, p. 3313 - 3316
  作者：Itazaki, Masumi、Ueda, Kensuke、Nakazawa, Hiroshi

  DOI：——

  日期：——
• Fukumoto, Kozo; Oya, Tsukuru; Itazaki, Masumi, Journal of the American Chemical Society, 2009, vol. 131, p. 38 - 39
  作者：Fukumoto, Kozo、Oya, Tsukuru、Itazaki, Masumi、Nakazawa, Hiroshi

  DOI：——

  日期：——