(2,6-((2,6-(diisopropyl)C₆H₃)N=C(CH₂)₃)₂C₅HN)Fe(N₂)₂ | 1426690-85-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2,6-((2,6-(diisopropyl)C₆H₃)N=C(CH₂)₃)₂C₅HN)Fe(N₂)₂
• 英文别名: (^iPr(TB)PDI)Fe(N₂)₂
• CAS: 1426690-85-8
• 化学式: C₃₇H₄₇FeN₇
• 分子量: 645.674
• InChiKey: TYLLZPUWGIKBBU-JPUNYGDRSA-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：

  1,5-已二烯 、 (2,6-((2,6-(diisopropyl)C₆H₃)N=C(CH₂)₃)₂C₅HN)Fe(N₂)₂ 以 正己烷 为溶剂， 反应 0.08h， 以83%的产率得到
  参考文献：
  名称：

  Synthesis and Electronic Structure of Bis(imino)pyridine Iron Metallacyclic Intermediates in Iron-Catalyzed Cyclization Reactions

  摘要：

  The bis(imino)pyridine iron dinitrogen compound, ((PDI)-P-iPr(TB))Fe(N-2)(2) ((iPr(TB)) PDI = 2,6-(2,6-Pr-i(2)-C6H3- N=C center dot(CH2)(3))(2)(C5H1N)) is an effective precatalyst for the [2 pi + 2 pi] cycloaddition of diallyl amines as well as the hydrogenative cyclization of N-tosylated enynes and diynes. Addition of stoichiometric quantities of amino-substituted enyne and diyne substrates to ((PDI)-P-iPr(TB))Fe(N-2)(2) resulted in isolation of catalytically competent bis(imino)pyridine iron metallacycle intermediates. A combination of magnetochemistry, X-ray diffraction, and Mossbauer spectroscopic and computational studies established S = 1 iron compounds that are best described as intermediate-spin iron(III) (S-Fe = 3/2) antiferromagnetically coupled to a chelate radical anion (S-PDI = 1/2). Catalytically competent bis(imino)pyridine iron diene and metallacycles relevant to the [2 pi + 2 pi] cycloaddition were also isolated and structurally characterized. The combined magnetic, structural, spectroscopic, and computational data support an Fe(I) Fe(III) catalytic cycle where the bis(imino)pyridine chelate remains in its one-electron reduced radical anion form. These studies revise a previous mechanistic proposal involving exclusively ferrous intermediates and highlight the importance of the redox-active bis(imino)pyridine chelate for enabling catalytic cyclization chemistry with iron.

  DOI：

  10.1021/ja400895j
• 作为产物：
  描述：

  (15E)-N-((E)-4-(2,6-diisopropylphenylimino)-1,2,3,4,7,8-hexahydroacridin-5(6H)-ylidene)-2,6-diisopropylbenzeneamine iron(II) chloride 、 氮 在 sodium amalgam 作用下， 以 甲苯 为溶剂， 反应 14.0h， 以61%的产率得到(2,6-((2,6-(diisopropyl)C₆H₃)N=C(CH₂)₃)₂C₅HN)Fe(N₂)₂
  参考文献：
  名称：

  Synthesis and Electronic Structure of Bis(imino)pyridine Iron Metallacyclic Intermediates in Iron-Catalyzed Cyclization Reactions

  摘要：

  The bis(imino)pyridine iron dinitrogen compound, ((PDI)-P-iPr(TB))Fe(N-2)(2) ((iPr(TB)) PDI = 2,6-(2,6-Pr-i(2)-C6H3- N=C center dot(CH2)(3))(2)(C5H1N)) is an effective precatalyst for the [2 pi + 2 pi] cycloaddition of diallyl amines as well as the hydrogenative cyclization of N-tosylated enynes and diynes. Addition of stoichiometric quantities of amino-substituted enyne and diyne substrates to ((PDI)-P-iPr(TB))Fe(N-2)(2) resulted in isolation of catalytically competent bis(imino)pyridine iron metallacycle intermediates. A combination of magnetochemistry, X-ray diffraction, and Mossbauer spectroscopic and computational studies established S = 1 iron compounds that are best described as intermediate-spin iron(III) (S-Fe = 3/2) antiferromagnetically coupled to a chelate radical anion (S-PDI = 1/2). Catalytically competent bis(imino)pyridine iron diene and metallacycles relevant to the [2 pi + 2 pi] cycloaddition were also isolated and structurally characterized. The combined magnetic, structural, spectroscopic, and computational data support an Fe(I) Fe(III) catalytic cycle where the bis(imino)pyridine chelate remains in its one-electron reduced radical anion form. These studies revise a previous mechanistic proposal involving exclusively ferrous intermediates and highlight the importance of the redox-active bis(imino)pyridine chelate for enabling catalytic cyclization chemistry with iron.

  DOI：

  10.1021/ja400895j
• 作为试剂：
  描述：

  N,N-二烯丙苯胺 在 (2,6-((2,6-(diisopropyl)C₆H₃)N=C(CH₂)₃)₂C₅HN)Fe(N₂)₂ 作用下， 以 氘代苯 为溶剂， 以100%的产率得到
  参考文献：
  名称：

  Synthesis and Electronic Structure of Bis(imino)pyridine Iron Metallacyclic Intermediates in Iron-Catalyzed Cyclization Reactions

  摘要：

  The bis(imino)pyridine iron dinitrogen compound, ((PDI)-P-iPr(TB))Fe(N-2)(2) ((iPr(TB)) PDI = 2,6-(2,6-Pr-i(2)-C6H3- N=C center dot(CH2)(3))(2)(C5H1N)) is an effective precatalyst for the [2 pi + 2 pi] cycloaddition of diallyl amines as well as the hydrogenative cyclization of N-tosylated enynes and diynes. Addition of stoichiometric quantities of amino-substituted enyne and diyne substrates to ((PDI)-P-iPr(TB))Fe(N-2)(2) resulted in isolation of catalytically competent bis(imino)pyridine iron metallacycle intermediates. A combination of magnetochemistry, X-ray diffraction, and Mossbauer spectroscopic and computational studies established S = 1 iron compounds that are best described as intermediate-spin iron(III) (S-Fe = 3/2) antiferromagnetically coupled to a chelate radical anion (S-PDI = 1/2). Catalytically competent bis(imino)pyridine iron diene and metallacycles relevant to the [2 pi + 2 pi] cycloaddition were also isolated and structurally characterized. The combined magnetic, structural, spectroscopic, and computational data support an Fe(I) Fe(III) catalytic cycle where the bis(imino)pyridine chelate remains in its one-electron reduced radical anion form. These studies revise a previous mechanistic proposal involving exclusively ferrous intermediates and highlight the importance of the redox-active bis(imino)pyridine chelate for enabling catalytic cyclization chemistry with iron.

  DOI：

  10.1021/ja400895j

文献信息

• Investigations into the Mechanism of Inter- and Intramolecular Iron-Catalyzed [2 + 2] Cycloaddition of Alkenes
  作者：Matthew V. Joannou、Jordan M. Hoyt、Paul J. Chirik

  DOI：10.1021/jacs.0c00250

  日期：2020.3.18

  catalytically relevant intermediates were used to gain insight into the mechanism of both inter- and intramolecular [2+2] cycloaddition reactions. For the stereo- and regioselective [2+2] cycloaddition of 1-octene to form trans-1,2-dihexylcyclobutane, a first-order dependence on both iron complex and alkene was measured as well as an inverse dependence on N2 pressure. Both 57Fe Mössbauer and infrared spectroscopic

  报道了由 (tricPDI)Fe(N2) (tricPDI = 2,6-(2,4,6-三环戊基)C6H2N=CMe)2C5H3N 促进的分子间和分子内 [2+2] 烯烃环加成形成环丁烷的机理研究）。结合动力学测量、冷冻淬火 57Fe Mössbauer 和红外光谱测量、氘标记研究、自然丰度 13C KIE 研究以及催化相关中间体的分离和表征，以深入了解分子间和分子内的机制 [2 +2] 环加成反应。对于 1-辛烯的立体和区域选择性 [2+2] 环加成形成反式-1,2-二己基环丁烷，测量了对铁配合物和烯烃的一级依赖性以及对 N2 压力的逆向依赖性。57Fe Mössbauer 和红外光谱测量均将 (tricPDI)Fe(N2)(η2-1-辛烯) 确定为催化剂静止状态。1-辛烯与 (tricPDI)Fe(η2-1-辛烯) 的决定速率关联解释了烯烃的一级依赖性和对 N2 的反向依赖性。重原子 13C/12C