{FeH(N2)(depe)2}BPh4 (depe=1,2-bis(diethylphosphino)ethane) | 26061-40-5

• 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: {FeH(N2)(depe)2}BPh4 (depe=1,2-bis(diethylphosphino)ethane)
• 英文别名: trans-{FeH(N2)(depe)2}B(C6H5)4；[trans-Fe(H)(N2)(Et2PCH2CH2PEt2)2][BPh4]；[trans-Fe(H)(N₂)(Et₂PCH₂CH₂PEt₂)₂][BPh₄]；trans-[FeH(N2)(1,2-bis(diethylphosphino)ethane)2]⁺[BPh4]^-；trans-[FeH(N2)(depe)₂]⁺[BPh4]^-
• CAS: 26061-40-5
• 化学式: C₂₀H₄₉FeN₂P₄*C₂₄H₂₀B
• 分子量: 816.598
• InChiKey: HZWKQAVYQSPJAK-UHFFFAOYSA-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：

  {FeH(N2)(depe)2}BPh4 (depe=1,2-bis(diethylphosphino)ethane) 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 生成 Fe(depe)2(N2)
  参考文献：
  名称：

  Teaching old compounds new tricks: efficient N₂ fixation by simple Fe(N₂)(diphosphine)₂ complexes

  摘要：

  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。

  DOI：

  10.1039/c6dt00884d
• 作为产物：
  描述：

  FeHCl(1,2-bis(diethylphosphino)ethane)₂ 、 四苯硼钠 在 N₂ 作用下， 以 甲醇 为溶剂， 以86%的产率得到{FeH(N2)(depe)2}BPh4 (depe=1,2-bis(diethylphosphino)ethane)
  参考文献：
  名称：

  Buys, Irmi E.; Field, Leslie D.; Hambley, Trevor W., Acta Crystallographica, Section C: Crystal Structure Communications, 1993, vol. 49, p. 1056 - 1059

  摘要：

  DOI：

文献信息

• 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。
• Mechanistic studies on iron phosphine complexes. Part 2. Protonation and substitution reactions of dinitrogen complexes
  作者：Richard A. Henderson

  DOI：10.1039/dt9880000515

  日期：——

  contrast, the mechanisms of the reactions of the nucleophiles L = CO, MeCN, or PhCN depend on the iron complex. Substitution of the bridged-dinitrogen ligand in trans-[FeCl(depe)2}2(µ-N2)]2+ occurs, in general, by two parallel pathways. After initial phosphine chelate ring opening the vacant site thus generated can be attacked either by a molecule of solvent or the nucleophile. Subsequent loss of dinitrogen

  酸（HCl或HBr）或亲核试剂CO，MeCN或PhCN与反式-[FeH（N 2）（depe）2 ] +和反式-[FeCl（depe）2 } 2（µ -N 2）] 2+（depe = Et 2 PCH 2 CH 2 PEt 2）已在四氢呋喃中研究（I = 0.1 mol dm –3，[NBu n 4 ] [BF 4]; 25.0°C）。在与酸的反应中，每个铁络合物的膦螯合环快速打开，可使侧链磷原子质子化，并最终失去膦配体。相反，亲核试剂L = CO，MeCN或PhCN的反应机理取决于铁配合物。反式-[FeCl（depe）2 } 2（µ-N 2）] 2+中桥二氮配体的取代通常通过两个平行途径发生。在最初的膦螯合物开环后，由此产生的空位可被溶剂分子或亲核试剂攻击。随后损失二氮和膦螯合环（对于溶剂途径，通过亲核体分子置换配位溶剂）产生反式-[FeCl（L）（depe）2 ] +的产物。尽管快速的膦螯合物开环反应与反式-[FeH（N
• 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：——
• Bautista, Maria; Earl, Kelly A.; Morris, Robert H., Journal of the American Chemical Society, 1987, vol. 109, p. 3780 - 3782
  作者：Bautista, Maria、Earl, Kelly A.、Morris, Robert H.、Sella, Andrea

  DOI：——

  日期：——