(η(5)-Cp)Fe(CO)(H)(PPh2Me) | 168841-57-4

• 英文名称: (η(5)-Cp)Fe(CO)(H)(PPh2Me)
• CAS: 168841-57-4
• 化学式: C₁₉H₁₉FeOP
• 分子量: 350.18
• InChiKey: JHCGECZVJJQLHB-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

• 作为反应物：
  描述：

  (η(5)-Cp)Fe(CO)(H)(PPh2Me) 、 以 氘代苯 为溶剂， 反应 0.08h， 以21%的产率得到
  参考文献：
  名称：

  Mixed phosphine/carbonyl derivatives of heterobimetallic copper–iron and copper–tungsten catalysts

  摘要：

  Evolution of dihydrogen was observed from reactions of protic metal-hydride complexes FeCp(CO)(PR3) H and WCp*(CO)(2)(PR3)H with hydridic (NHC)CuH complexes, providing access to several heterobimetallic (NHC)Cu-FeCp(CO)(PR3) and (NHC)Cu-WCp*(CO)(2)(PR3) complexes that are the mixed phosphine/ carbonyl derivatives of previously studied catalysts for C-H borylation (NHC = N-heterocyclic carbene). The new complexes were characterized by multinuclear NMR spectroscopy, FT-IR spectroscopy, and in some cases X-ray crystallography. In one case, a (NHC)Cu(mu(2) -H)(2)FeCp(PPh3) complex was structurally characterized as the decomposition product of an unstable (NHC)Cu-FeCp(CO)(PPh3) derivative. Preliminary trials in C-H borylation catalysis are reported, including measurable activity under photochemical conditions. (C) 2018 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2018.09.062
• 作为产物：
  描述：

  (η5-C5H5)Fe(CO)(PMePh2)I 、 sodium tetrahydroborate 以 四氢呋喃 为溶剂， 生成 (η(5)-Cp)Fe(CO)(H)(PPh2Me)
  参考文献：
  名称：

  Mixed phosphine/carbonyl derivatives of heterobimetallic copper–iron and copper–tungsten catalysts

  摘要：

  Evolution of dihydrogen was observed from reactions of protic metal-hydride complexes FeCp(CO)(PR3) H and WCp*(CO)(2)(PR3)H with hydridic (NHC)CuH complexes, providing access to several heterobimetallic (NHC)Cu-FeCp(CO)(PR3) and (NHC)Cu-WCp*(CO)(2)(PR3) complexes that are the mixed phosphine/ carbonyl derivatives of previously studied catalysts for C-H borylation (NHC = N-heterocyclic carbene). The new complexes were characterized by multinuclear NMR spectroscopy, FT-IR spectroscopy, and in some cases X-ray crystallography. In one case, a (NHC)Cu(mu(2) -H)(2)FeCp(PPh3) complex was structurally characterized as the decomposition product of an unstable (NHC)Cu-FeCp(CO)(PPh3) derivative. Preliminary trials in C-H borylation catalysis are reported, including measurable activity under photochemical conditions. (C) 2018 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2018.09.062

文献信息

• Mechanism of Alkyl Migration from Oxygen to Metal in Iron-Manganese Ethoxycarbyne Complexes. Induction of Postcleavage Intermolecular Ethyl Exchange by Hydride Bridging of Mononuclear Iron Species
  作者：Hamid Idmoumaz、Chien-Hsing Lin、William H. Hersh

  DOI：10.1021/om00009a008

  日期：1995.9

  The iron-manganese ethoxycarbyne Cp(CO)Fe(mu-COCH2CH3)(mu-CO)Mn(CO)MeCp (2a) undergoes thermal decomposition at 65 degrees C to give MeCpMn(CO)(3) and, in the presence of PPh(2)Me, CpFe(CO)(PPh(2)Me) CH2CH3 (4a). The reaction is first order in carbyne and zero order in phosphine and exhibits a kinetic deuterium isotope effect k(H)/k(D) = 2.0 +/- 0.1 Crossover experiments between 2a and its bis MeCp, CD2CD3 analog (2b-d(5)) or between 2a-d(5) and 2b result in scrambling of the alkyl label between products 4a and 4a-d(5) and their MeCp analogs 4b and 4b-d(5). A crossover experiment between 2a and 2b-C-13 labeled specifically at the ethoxy methylene carbon gave complete C-13 exchange in the methylene carbons of 4a,b but no C-13 exchange in the starting materials after 50% conversion and no C-13 scrambling into the methyl position of 4a,b. Ethylene does not affect the rate of decomposition of 2b or 2b-d(5), does not affect ethyl scrambling, and is not incorporated into 4b during the decomposition of 2b-d(5), ruling out ethylene rather than ethyl exchange. The course of the reaction between 2a and 2b-d(5) is not altered by the additives 2,6-di-tert-butyl-4-methoxyphenol, galvinoxyl, or thiophenol, ruling out involvement of radicals. ''Control crossover'' experiments between 2a-d(5) and 4b and between 2b-d(5) and 4a give no exchange. However, the iron hydride RC(5)H(4)Fe(CO)(PPh(2)Me)H (R = H, 5a; R = Me, 5b) forms by beta-elimination from RCpFe(CO)CH2CH3 followed by PPh(2)Me displacement of ethylene, and alkyl. exchange occurs when 2b and 5a are combined under the reaction conditions but not when 4b and 5a are combined. A mechanism for ethyl exchange is described in which catalytic amounts of 5a, 5b, and deuterated analogs 59-d(1) and 5b-d(1) intercept the 16-electron carbyne decomposition intermediates CpFe(CO)CH2CH3, MeCpFe(CO)CH2CH3, and their C2D5 analogs to give hydride-bridged species. Concomitant migration of the ethyl group and the PPh(2)Me ligand between the two iron atoms in these bridged species followed by cleavage to regenerate the hydride and 16-electron intermediate completes the exchange event. Slower trapping of the 16-electron intermediates by PPh(2)Me irreversibly removes them from the catalytic cycle, giving products 4a,b, 4a-d(5), and 4b-d(5).