FeH2(tris[2-(dimethylphosphino)ethyl]phosphine) | 189447-26-5

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: FeH2(tris[2-(dimethylphosphino)ethyl]phosphine)
• 英文别名: cis-[Fe(tris(2-dimethylphosphino)ethyl)phosphine)2H2]；FeH2(P(CH2CH2PMe2)3)；iron dihydride;tris(2-dimethylphosphanylethyl)phosphane
• CAS: 189447-26-5
• 化学式: C₁₂H₃₂FeP₄
• 分子量: 356.128
• InChiKey: RJIRWORBDVWECV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.15
• 重原子数：
  17.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  羰基硫 、 FeH2(tris[2-(dimethylphosphino)ethyl]phosphine) 以 苯 为溶剂， 以67%的产率得到cis-hydrido(thioformato)(tris(2-(dimethylphosphino)ethyl)phosphine)iron(II)
  参考文献：
  名称：

  将CO2，CS2和COS插入氢化铁（II）键中。

  摘要：

  cis-Fe（dmpe）2H2（dmpe = Me2PCH2CH2PMe2）（1）或cis-Fe（PP3）H2（PP3 = P（CH2CH2PMe2）3）（2）与二氧化碳（CO2），二硫化碳（CS2）之间的反应，并研究了羰基硫（COS）。在300 K下，向1中添加CO2（1 atm），CS2（2当量）和COS（1 atm）会形成稳定的氢化氢化物，反式Fe（dmpe）2（OCHO）H（3a）分别是反式-二硫代甲酰氢化物，反式-Fe（dmpe）2（SCHS）H（4a）和反式-硫代甲酰化氢，反式-Fe（dmpe）2（SCHO）H（5a）。当在195 K下将CS2和COS添加到顺式Fe（dmpe）2H2中时，最初形成的产物分别是顺式-二硫代甲酰氢4b和顺式-硫代甲酰氢5b，但没有证据。将CO2加到顺式Fe（dmpe）2H2中时，相应的顺式甲酰化氢的生成量。添加过量的CO2，CS2，且在较低温度（195-240

  DOI：

  10.1021/ic991399z
• 作为产物：
  描述：

  tris[2-(dimethylphosphino)ethyl]phosphine 以 四氢呋喃 为溶剂， 生成 FeH2(tris[2-(dimethylphosphino)ethyl]phosphine)
  参考文献：
  名称：

  Iron Complexes Containing the Tripodal Tetraphosphine Ligand P(CH₂CH₂PMe₂)₃

  摘要：

  The preparation and characterization of iron(II) complexes containing the tripodal tetraphosphine ligand tris[2-(dimethylphosphino)ethyl]phosphine, P(CH2CH2PMe2)(3) (PP3, 1), are reported. The complex FeCl2(PP3) (2) was formed by the reaction of PP3 with anhydrous iron(II) chloride. The complexes FeHCl(PP3) (3) and FeH2(PP3) (4) were formed by the reaction of 2 with Lithium aluminum hydride. Likewise, the complexes FeMeCl(PP3) (5) and FeMe2(PP3) (6) were formed by the reaction of 2 with methyllithium or dimethylmagnesium. Reaction of 2 with CO afforded a mixture of isomeric carbonyl chloride complexes [Fe(CO)Cl(PP3)](+) (7 and 8). Reaction of 2 with PPh3 afforded. [Fe(PPh3)Cl(PP3)](+) (9). The air-sensitive complexes 2-9 were characterized by multinuclear NMR spectroscopy, and 9 was characterized by X-ray crystallography. Crystals of 9 (BPh4 salt), C54H65BClFeP5, M971.09, arts monoclinic, space group P2(1)/c, a = 13.246(3) Angstrom, b = 30.314(2) Angstrom, c = 14.338(2) Angstrom, beta = 100.92(2)degrees, Z = 4; R = 0.058.

  DOI：

  10.1021/ic970030b

文献信息

• An iron(ii) dihydrogen hydrido complex containing the tripodal tetraphosphine ligand P(CH2CH2PMe2)3
  作者：Leslie D. Field、Hsiu L. Li、Barbara A. Messerle、Ronald J. Smernik、Peter Turner

  DOI：10.1039/b401954g

  日期：——

  complex FeH2(PP3) 3 with methanol or ethanol. The observation of H–D coupling in partially deuterated isotopomers of 1 and measurement of T1 relaxation times for the hydrido and dihydrogen resonances of 1 confirmed the presence of the η2-dihydrogen ligand. Complex 1 shows dynamic NMR behaviour in both the 31P and 1H NMR spectra with facile exchange between the protons in the η2-dihydrogen ligand and the

  二氢盐氢基络合物[FEH（H 2）（PP 3）] + 1 （PP 3 = P（CH 2 CH 2 PME 2）3 2）通过dihydrido的质子化复杂FEH形成2（PP 3） 3与甲醇或乙醇。H-d耦合在部分氘化同位素的观察1的和测量Ť 1弛豫时间的氢基和二氢共振1证实了η存在2 -dihydrogen配体。综合大楼1示出了在两个动态NMR行为31 P和1 1 H NMR谱与在η的质子之间容易交换2 -dihydrogen配体和η 1 -hydrido配体。的二氢配体1容易通过阴离子和中性配位体置换，得到相应的氢基配合物[FeHX（PP 3）] + （X = CO 11，X = PPH 3 12）或FeHX（PP 3）（X =氯13，X ＝ Br 14，X ＝ I 15，X ＝ N 3 16）。少量烷氧基氢化物FeH（OR）（PP3）在含有1的甲醇和乙醇溶液中观察到（R = Me 4 ;
• Addition of Nitrogen-Containing Heteroallenes to Iron(II)-Hydrides
  作者：Leslie D. Field、Warren J. Shaw、Peter Turner

  DOI：10.1021/om0100030

  日期：2001.8.1

  P(CH2CH2PMe2)3) (2) and phenyl isothiocyanate (PhNCS), ethyl isothiocyanate (EtNCS), and phenyl isocyanate (PhNCO) were investigated. PhNCS reacts with 1 to form a variety of insertion products at low temperature, and the thermodynamic product hydridoiron N-phenylthioformimidate trans-Fe(dmpe)2(SCHNPh)H (3a) at 300 K. Addition of an excess of PhNCS to 1 produces the bis(insertion) product trans-Fe(dmpe)2(SCHNPh)2

  之间的反应顺-Fe（DMPE）2 ħ 2（DMPE =我2 PCH 2 CH 2 PME 2）（1）或顺式-Fe（PP 3）H 2（PP 3 = P（CH 2 CH 2 PME 2）3）（2）研究了异硫氰酸苯酯（PhNCS），异硫氰酸乙酯（EtNCS）和异氰酸苯酯（PhNCO）。PhNCS在低温下与1反应形成各种插入产物，而热力学产物氢化铁N-苯硫基甲亚氨酸酯反式-Fe（DMPe）2（SCHNPh）H（3a）在300K。将过量的PhNCS加到1产生双（插入）产物反式-Fe（DMPe）2（SCHNPh）2（3c）。EtNCS插入1的铁氢键中，形成反式-Fe（DMPe）2（SCHNEt）H（4a，热力学乘积）和顺式-Fe（DMPe）2（SCHNEt）H（4b，动力学乘积）。添加过量的EtNCS不会导致第二次插入，而是会攻击硫代甲酰胺基配体以形成反式-Fe（DMPe）2（SCHN +（Et）C（S）N
• A quantitative measure of the ionicity of selected iron hydride species by examination of the deuterium quadrupole coupling constant (DQCC)
  作者：Leslie D. Field、Warren J. Shaw、Guy K.B. Clentsmith

  DOI：10.1016/j.jorganchem.2007.03.024

  日期：2007.6

  The ionicity of the metal hydride bonds of a series of iron hydrides supported by multidentate phosphine donors has been determined by means of DQCC measurements of the isotopically labelled hydrides in concentrated solution in toluene. (C) 2007 Elsevier B.V. All rights reserved.
• Mixed-Valence Dinitrogen-Bridged Fe(0)/Fe(II) Complex
  作者：Leslie D. Field、Ruth W. Guest、Peter Turner

  DOI：10.1021/ic101646p

  日期：2010.10.4

  The reactions of a dinitrogen-bridged Fe(II)/Fe(II) complex [(FeH(PP3))(2)(mu-N-2)](2+) (3) (PP3 = P(CH2CH2PMe2)(3)) with base were investigated usin N-15 labeling techniques to enhance characterization. In the presence of base, 3 is initially deprotonated to the Fe(II)/Fe(0) dinitrogen-bridged complex [(FeH(PP3))(kt-N-2)(Fe(PP3))]' (4) and then to the symmetrical Fe(0)/Fe(0) dinilrogen-bridged complex (Fe(PP3))(2)(u-N-2) (5). [(FeH(PP3))(j4-N2)(Fe(PP3))](+) (4) exhibits unusual long-range 31P-31P NMR coupling through the bridging dinitrogen ligand from the phosphines at the Fe(0) center and those at the Fe(II) center. Reaction of 4 with base under an atmosphere of argon resulted in the known dinitrogen Fe(0) complex Fe(N-2)(PP3) (6) and a solvent C H activation product. Complexes 3, 4, and 5 were fully characterized by multinuclear NMR spectroscopy, and complexes 3 and 4 by X-ray crystallography.