[trans-Fe(H)(N₂)(Me₂PCH₂CH₂PMe₂)₂][BPh₄] | 130172-19-9

• 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: [trans-Fe(H)(N₂)(Me₂PCH₂CH₂PMe₂)₂][BPh₄]
• 英文别名: trans-[FeH(N2)(1,2-bis(dimethylphosphino)ethane)2]+[BPh4]-；trans-[FeH(N2)(dmpe)2]+[BPh4]-
• CAS: 130172-19-9
• 化学式: C₁₂H₃₃FeN₂P₄*C₂₄H₂₀B
• 分子量: 704.383
• InChiKey: RBSIOKFZGDQSMM-UHFFFAOYSA-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：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [trans-Fe(H)(N₂)(Me₂PCH₂CH₂PMe₂)₂][BPh₄] 在 KOC(CH₃)3 作用下， 以 四氢呋喃 为溶剂， 生成 Fe(Me2PCH2CH2PMe2)2(N2)
  参考文献：
  名称：

  Bis[1,2-bis(dimethylphosphino)ethane]dihydrogenhydridoiron(II) tetraphenylborate as a model for the function of nitrogenases

  摘要：

  The trihydride complex [FeH3(dmpe)2]+ (dmpe = Me2PCH2CH2PMe2) is best represented as [FeH(H2)(dmpe2]+, with the H-H separation in the H-2 being ca. 0.81 angstrom. The H-2 can be replaced by N2, CO, MeCN, MeNC and C2H4. The dinitrogen complex [FeH(N2)(dmpe)2]+ may be deprotonated to yield the solution-stable, trigonal-bipyramidal species [Fe(N2)(dmpe)2], which can be reprotonated by HCl to yield [FeCl2(dmpe)2], N2, H-2, and NH3. The crystal structures of [FeH(H2)(dmpe)2]BPh4 and [FeH(N2)(dmpe)2]BPh4 have been determined.

  DOI：

  10.1039/dt9930003041
• 作为产物：
  描述：

  {FeH(H2)(dmpe)2}BPh4 (dmpe=1,2-bis(dimethylphosphino)ethane) 在 N₂ 作用下， 以 四氢呋喃 为溶剂， 以>99的产率得到[trans-Fe(H)(N₂)(Me₂PCH₂CH₂PMe₂)₂][BPh₄]
  参考文献：
  名称：

  Bis[1,2-bis(dimethylphosphino)ethane]dihydrogenhydridoiron(II) tetraphenylborate as a model for the function of nitrogenases

  摘要：

  The trihydride complex [FeH3(dmpe)2]+ (dmpe = Me2PCH2CH2PMe2) is best represented as [FeH(H2)(dmpe2]+, with the H-H separation in the H-2 being ca. 0.81 angstrom. The H-2 can be replaced by N2, CO, MeCN, MeNC and C2H4. The dinitrogen complex [FeH(N2)(dmpe)2]+ may be deprotonated to yield the solution-stable, trigonal-bipyramidal species [Fe(N2)(dmpe)2], which can be reprotonated by HCl to yield [FeCl2(dmpe)2], N2, H-2, and NH3. The crystal structures of [FeH(H2)(dmpe)2]BPh4 and [FeH(N2)(dmpe)2]BPh4 have been determined.

  DOI：

  10.1039/dt9930003041

文献信息

• Teaching old compounds new tricks: efficient N₂ fixation by simple Fe(N₂)(diphosphine)₂ complexes
  作者：Laurence R. Doyle、Peter J. Hill、Gregory G. Wildgoose、Andrew E. Ashley

  DOI：10.1039/c6dt00884d

  日期：——

  The Fe(0) species Fe(N₂)(dmpe)₂ exists in equilibrium with the previously unreported dimer, [Fe(dmpe₂)₂(μ-N₂)]. For the first time these complexes, alongside Fe(N₂)(depe)₂, are shown unambiguously to produce N₂H₄ and/or NH₃ upon addition of triflic acid; for Fe(N₂)(depe)₂ this represents one of the highest electron conversion efficiencies for Fe complexes to date.

  Fe(N₂)(dmpe)₂物种与先前未报告的二聚体[Fe(dmpe₂)₂(μ-N₂)]处于平衡状态。这些配合物首次清晰地显示出，与Fe(N₂)(depe)₂一起，在加入三氟甲磺酸后产生N₂H₄和/或NH₃；对于Fe(N₂)(depe)₂来说，这代表迄今为止Fe配合物中最高的电子转化效率之一。
• Reduction of dinitrogen bound at an iron(0) centre
  作者：David A. Hall、G. Jeffery Leigh

  DOI：10.1039/dt9960003539

  日期：——

  It has been confirmed that the deprotonation–reprotonation of dinitrogeniron(II) complexes is a method of producing limited amounts of ammonia. However, the original postulate that such reactions involve an iron(0) dinitrogen complex as the key intermediate may be in error. The species originally identified as such is much more likely to have been a hydrido-complex impurity, and the ammonia-yielding intermediate remains uncharacterised.

  现已证实，二氮铁（II）络合物的去质子化-再质子化反应是产生少量氨的一种方法。不过，最初认为此类反应的关键中间体是二氮铁(0)络合物的推测可能有误。最初被认定为二氮铁络合物的物种更有可能是一种氢化物络合物杂质，而产生氨的中间体仍未定性。
• Complexes of tertiary phosphines with iron(II) and dinitrogen, dihydrogen, and other small molecules
  作者：Adrian Hills、David L. Hughes、Manuel Jimenez-Tenorio、G.Jeffery Leigh

  DOI：10.1016/0022-328x(90)85070-f

  日期：1990.8

  produces the hydrides [FeH3(diphosphine)2]+ in high yield. These complexes react with a variety of small molecules including N2 to give further complexes. CO2 and CS2 insert into the iron hydride bond to yield formato- and dithioformato-complexes, respectively, and carboxymethyl acetylene and phenyl acetylene yield a cyclic alkenyl complex and an acetylide, respectively.

  的治疗[的FeCl 2（二膦）2 ]在乙醇中与硼氢化钠产生氢化物[FEH 3（二膦）2 ] +中高收率。这些配合物与包括N 2在内的各种小分子反应生成进一步的配合物。CO 2和CS 2插入到氢化铁键中，分别生成甲酸酯和二硫代甲酸酯络合物，而羧甲基乙炔和苯基乙炔分别生成环状烯基络合物和乙炔化物。
• Nitrogen Fixation Revisited on Iron(0) Dinitrogen Phosphine Complexes
  作者：Leslie D. Field、Nilay Hazari、Hsiu L. Li

  DOI：10.1021/acs.inorgchem.5b00211

  日期：2015.5.18

  A reinvestigation of the treatment of [Fe(N-2)(PP)(2)] (PP = depe, dmpe) with acid revealed no ammonium formation. Instead, rapid protonation at the metal center to give hydride Complexes was observed. Treatment of [Fe(N-2)(dmpe)(2)] with methylating agents such as methyl triflate or methyl tosylate resulted methylation of the metal center to afford [FeMe(N-2)(dmpe)(2)](+). Treatment of [Fe(N-2)(dmpe)(2)] With trimethylsilyl triflate, however, resulted in reactibn at dinitrogen affording NH4+ on subsequent treatment with acid. The side-on bound hydrazine complex [Fe-(N2H4)(dmpe)(2)](2+) and bis(ammonia) complex [Fe(NH3)(2)(dmpe)(2)](2+) were identified by N-15 NMR spectroscopy as other species formed in the reaction mixture.
• Helleren, Caroline A.; Henderson, Richard A.; Leigh, G. Jeffery, Journal of the Chemical Society, Dalton Transactions, 1999, # 8, p. 1213 - 1220
  作者：Helleren, Caroline A.、Henderson, Richard A.、Leigh, G. Jeffery

  DOI：——

  日期：——