tetracarbonyl(η2-dimethyl fumarate)iron | 12287-98-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: tetracarbonyl(η2-dimethyl fumarate)iron
• 英文别名: tetracarbonyl(η-dimethyl fumarate)iron；Fe(CO)4(η2-dimethyl fumarate)；dimethyl fumarate tetracarbonyliron complex
• CAS: 12287-98-8；109468-38-4
• 化学式: C₁₀H₈FeO₈
• 分子量: 312.016
• InChiKey: BITDAGYZFCHFJO-XIOYJQOGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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

• 作为反应物：
  描述：

  tetracarbonyl(η2-dimethyl fumarate)iron 在 氢气 作用下， 以 polyethylene 为溶剂， 生成 五羰基铁
  参考文献：
  名称：

  A New Approach To Studying the Mechanism of Catalytic Reactions:  An Investigation into the Photocatalytic Hydrogenation of Norbornadiene and Dimethylfumarate Using Polyethylene Matrices at Low Temperature and High Pressure

  摘要：

  This paper presents a new method for investigating the mechanisms of homogeneously catalyzed reactions involving gases, particularly H-2. We show how the combination of polyethylene (PE) matrices and high pressure-low temperature (HPLT) experiments can be used to provide new mechanistic information on hydrogenation processes. In particular, we show how we are able to generate reaction intermediates at low temperature, and then to extract the contents of the PE film at room temperature to characterize the organic products using GC-MS, We have used our new technique to probe both the hydrogenation of dimethyl fumarate (DF), using Fe(CO)(4)(eta (2)-DF) as the catalytic species, and the hydrogenation of norbornadiene (NBD), using (NBD)M(CO)(4) (M = Cr or Mo) as the catalytic species. Irradiation of Fe(CO)(4)(eta (2)-DF) in a PE matrix at 150 K resulted in the formation of an intermediate complex tentatively assigned Fe(CO)(3)(eta (4)-DF). Warming this complex to 260 K under H-2 leads to the formation of Fe(CO)(3)(eta (2)-DF)(eta (2)-H-2). Further warming of the reaction system results in the hydrogenation of the coordinated DF, to generate dimethyl succinate (DS), Characterization of the intermediate species was obtained using FTIR spectroscopy. Formation of DS was confirmed using both FTIR spectroscopy and GC-MS analysis. UV photolysis of (NBD)M(CO)I in PE under H-2 in the presence of excess NBD results in the formation of the hydrogenated products norbornene (NBN) and nortricyclene (NTC), with trace amounts of norbornane (NBA) being observed. These products were in similar ratios to those observed in fluid solution. However, for (NBD)Mo(CO)(4), the relative amounts of the organic products change considerably when the reaction is repeated in PE under H-2 in the absence of free NBD, with NEA being the major product. The use of our HPLT cell allows us to vent and exchange high pressures of gases with ease, and as such we have performed gas exchange reactions with H-2 and D-2. Analysis of the reaction products from these exchange reactions with GC-MS provides evidence for the mechanism of formation of NEA, in both the presence and absence of excess NBD, a reaction which has been largely ignored in previous studies.

  DOI：

  10.1021/ja004345t
• 作为产物：
  描述：

  diiron nonacarbonyl 、 富马酸二甲酯 以 乙醚 为溶剂， 反应 18.0h， 以81%的产率得到tetracarbonyl(η2-dimethyl fumarate)iron
  参考文献：
  名称：

  富马酸甲酯衍生的铁羰基配合物（FumET-CORM）作为强效抗炎药。

  摘要：

  自身免疫性疾病的特征在于树突状细胞（DC）驱动的促炎性T细胞反应的激活。这些严重疾病的治疗选择包括小分子，例如富马酸二甲酯，或“气体递质”，例如CO。在此，我们描述了双功能酶触发的CO释放分子（ET-CORM）的合成，该酶可同时在细胞内释放两种CO和富马酸甲酯。使用骨髓衍生的DC，这些富马酸甲酯衍生的化合物（FumET-CORMs）的治疗潜力令人印象深刻，这是通过强烈抑制脂多糖诱导的促炎性信号通路和阻断下游白介素12或-23的产生来证明的。数据还表明，FumET-CORMs能够将DC转化为抗炎表型。因此，

  DOI：

  10.1002/cmdc.201700488

文献信息

• Reactions of tetracarbonyihydridoferrate(<scp>0</scp>) with acetylenes in aprotic solvents: (1—3-η-acryloyl)tricarbonylferrates and tricarbonyl(1—3-η-prop-2-en-1-ylidene)iron complexes
  作者：Take-aki Mitsudo、Yoshihisa Watanabe、Hiroshi Nakanishi、Lsao Morishima、Toshiro Inubushi、Yoshinobu Takegami

  DOI：10.1039/dt9780001298

  日期：——

  The ion [FeH(CO)4]– reacts with acetylenes, HCCCOR (R = OMe, Me, or H) or MeO2CCCCO2Me, to give [ Fe(η3- H R1CCR2CO)(CO)3]3(3) by trans addition of the hydride to the acetylenic bond. Protonation of (3) gives [Fe(η-HR1CCR2H)(CO)4](5) by an intramolecular decarbonylation reaction. Methylation of (3a; R1= H, R2= CO2Me) and (3b; RI= R2= CO2Me) with SFO2(OMe) or [OMe3][BF4] gives [Feη3-C(OMe)C(CO2Me)CH2}(CO)3](6a)

  离子[FEH（CO）4 ] -发生反应与乙炔，HC CCOR（R = OME，Me或H）或的MeO 2 CC CCO 2 Me中，得到的[Fe（η 3 - HR 1 C ^ CR 2 CO）（通过将氢化物反式加成到炔键上，得到CO）3 ] 3（3）。（3）质子化给出的[Fe（η-HR 1 C ^ CR 2 H）（CO）4 ]（5）通过分子内脱羰反应。（3a; R 1 = H，R 2 = CO 2 Me）和（3b; R I = R 2的甲基化= CO 2 Me）的与SFO 2（OME）或[OME 3 ] [BF 4 ]给出的[Fe η 3 -C（OME）C（CO 2 Me）的CH 2 }（CO）3 ]（6a）和的[Fe η 3 -反式-C（OME）C（CO 2 Me）的C（CO 2 Me）的H}（CO）3 ]（6b）中。的（图6a）的氧化和（6b）中与吡啶/ Ñ氧化物给出的[Fe η-H
• Gerhartz, Wolfgang; Grevels, Friedrich-Wilhelm; Klotzbücher, Werner E., Organometallics, 1987, vol. 6, # 9, p. 1850 - 1856
  作者：Gerhartz, Wolfgang、Grevels, Friedrich-Wilhelm、Klotzbücher, Werner E.

  DOI：——

  日期：——