[(((2,6-CHMe2)2C6H3N=CMe)2C5H3N)Fe(η2-H2)] | 799270-33-0

• 英文名称: [(((2,6-CHMe2)2C6H3N=CMe)2C5H3N)Fe(η2-H2)]
• 英文别名: [(2,6-(i-Pr)2C6H3N=CMe)2C5H3N)Fe(H2)]
• CAS: 799270-33-0
• 化学式: C₃₃H₄₅FeN₃
• 分子量: 539.587
• InChiKey: LTINPHRVSMSLBS-DGOWAXEKSA-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：
  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：

  [(((2,6-CHMe2)2C6H3N=CMe)2C5H3N)Fe(η2-H2)] 以 not given 为溶剂， 生成 [(2,6-(i-Pr)2C6H3N=CMe)2C5H3N)Fe(2,5-(t-Bu)2C6H3N)]
  参考文献：
  名称：

  Synthesis and Hydrogenation of Bis(imino)pyridine Iron Imides

  摘要：

  Treatment of the iron bis(dinitrogen) complex, (iPrPDI)Fe(N2)2 (iPrPDI = (2,6-iPr2C6H3N=CMe)2C5H3N), with a series of aryl azides resulted in loss of 3 equiv of N2 and formation of the corresponding four-coordinate iron imide compounds, (iPrPDI)Fe(NAr). These complexes, two of which (Ar = 2,6-iPr2-C6H3 and 2,4,6-Me3-C6H2) have been characterized by X-ray diffraction, are significantly distorted from planarity. The metrical parameters in combination with Mössbauer spectroscopic and SQUID magnetic data suggest an intermediate spin iron(III) center antiferromagnetically coupled to a ligand-centered radical. Nitrene group transfer has been accomplished by addition of 1 atm of CO, yielding aryl isocyanates, ArNCO, and (iPrPDI)Fe(CO)2. Hydrogenation of the more sterically hindered members of the series furnished free aniline and the previously reported iron dihydrogen complex. Catalytic aryl azide hydrogenation has also been achieved, and the observed relative rates are consistent with N-H bond formation as the rate-determining step in aniline formation.

  DOI：

  10.1021/ja057165y
• 作为产物：
  描述：

  (iPrPDI)Fe(N2)2 以 氘代苯 为溶剂， 生成 [(((2,6-CHMe2)2C6H3N=CMe)2C5H3N)Fe(η2-H2)]
  参考文献：
  名称：

  Synthesis and Hydrogenation of Bis(imino)pyridine Iron Imides

  摘要：

  Treatment of the iron bis(dinitrogen) complex, (iPrPDI)Fe(N2)2 (iPrPDI = (2,6-iPr2C6H3N=CMe)2C5H3N), with a series of aryl azides resulted in loss of 3 equiv of N2 and formation of the corresponding four-coordinate iron imide compounds, (iPrPDI)Fe(NAr). These complexes, two of which (Ar = 2,6-iPr2-C6H3 and 2,4,6-Me3-C6H2) have been characterized by X-ray diffraction, are significantly distorted from planarity. The metrical parameters in combination with Mössbauer spectroscopic and SQUID magnetic data suggest an intermediate spin iron(III) center antiferromagnetically coupled to a ligand-centered radical. Nitrene group transfer has been accomplished by addition of 1 atm of CO, yielding aryl isocyanates, ArNCO, and (iPrPDI)Fe(CO)2. Hydrogenation of the more sterically hindered members of the series furnished free aniline and the previously reported iron dihydrogen complex. Catalytic aryl azide hydrogenation has also been achieved, and the observed relative rates are consistent with N-H bond formation as the rate-determining step in aniline formation.

  DOI：

  10.1021/ja057165y
• 作为试剂：
  描述：

  1,5-已二烯 在 [(((2,6-CHMe2)2C6H3N=CMe)2C5H3N)Fe(η2-H2)] 作用下， 以 氘代苯 为溶剂， 生成 亚甲基环戊烷
  参考文献：
  名称：

  Iron-Catalyzed [2π + 2π] Cycloaddition of α,ω-Dienes:  The Importance of Redox-Active Supporting Ligands

  摘要：

  The bis(imino)pyridine iron bis(dinitrogen) complex, (iPrPDI)Fe(N2)2 (iPrPDI = 2,6-(2,6-iPr2C6H3NCR)2C5H3N), serves as an efficient precursor for the catalytic [2pi + 2pi] cycloaddition of alpha,omega-dienes to yield the corresponding bicycles. For amine substrates, the rate of catalytic turnover increases with the size of the nitrogen substituents, demonstrating competing heterocycle coordination and product inhibition. In one case, a bis(imino)pyridine iron azobicycloheptane product was characterized by X-ray diffraction. Preliminary mechanistic studies highlight the importance of the redox activity of the bis(imino)pyridine ligand to maintain the ferrous oxidation state throughout the catalytic cycle.

  DOI：

  10.1021/ja064711u

文献信息

• Preparation and Molecular and Electronic Structures of Iron(0) Dinitrogen and Silane Complexes and Their Application to Catalytic Hydrogenation and Hydrosilation
  作者：Suzanne C. Bart、Emil Lobkovsky、Paul J. Chirik

  DOI：10.1021/ja046753t

  日期：2004.10.1

  of the five-coordinate iron(II) dihalide complexes (iPrPDI)FeX2 (iPrPDI = ((2,6-CHMe2)2C6H3N=CMe)2C5H3N; X = Cl, Br) with sodium amalgam under 1 atm of dinitrogen afforded the square pyramidal, high spin iron(0) bis(dinitrogen) complex (iPrPDI)Fe(N2)2. In solution, (iPrPDI)Fe(N2)2 loses 1 equiv of N2 to afford the mono(dinitrogen) adduct (iPrPDI)Fe(N2). Both dinitrogen compounds serve as effective precatalysts

  五配位铁 (II) 二卤化物络合物 (iPrPDI)FeX2 (iPrPDI = ((2,6-CHMe2)2C6H3N=CMe)2C5H3N; X = Cl, Br) 在 1 个大气压的二氮下用钠汞合金还原得到正方形金字塔形，高自旋铁（0）双（二氮）络合物（iPrPDI）Fe（N2）2。在溶液中，(iPrPDI)Fe(N2)2 失去 1 当量的 N2 以提供单（二氮）加合物 (iPrPDI)Fe(N2)。这两种二氮化合物都可作为烯烃和炔烃加氢和硅氢化的有效预催化剂。在环境温度下，在非极性介质中使用低催化剂负载量（< 或 = 0.3 mol%）观察到有效的催化反应。催化氢化硅烷化在形成抗马尔科夫尼科夫产物方面具有选择性。