trans-Fe(depe)₂I₂ | 23041-90-9

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: trans-Fe(depe)₂I₂
• CAS: 23041-90-9
• 化学式: C₂₀H₄₈FeI₂P₄
• 分子量: 722.152
• InChiKey: FRGVTXGGNZAHTL-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  9.83
• 重原子数：
  27.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• 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：

  trans-Fe(depe)₂I₂ 在 CO 作用下， 以 甲醇 为溶剂， 以60%的产率得到trans-bis[1,2-bis(diethylphosphino)ethane]carbonyliodoiron(II) iodide
  参考文献：
  名称：

  阳离子低纺双[1,2-双（二烷基膦基）乙烷]铁（II）配合物

  摘要：

  复合物的反式- [的FeCl 2（DEPE）2 ]和反式- [的FeCl 2（DMPE）2 ]（DEPE =的Et 2 PCH 2 CH 2 PET 2，DMPE =我2 PCH 2 CH 2 PME 2）溶解在乙腈和甲醇制得1：1电解质。在甲醇溶液中，反式-[FeCl 2（depe）2 ]与各种π受体配体快速反应，生成反式-[FeCl（L）（depe）2 ] +的阳离子[L ＝ CO，NO +，RCN，1 / 2N 2和P（OMe）3 ]已经分离为其四苯基硼酸盐或氯化物盐。在丙酮溶液中，中性配合物的反应要慢得多，并且配体L的范围更小。如果发生反应（L = CO或RNC），则会得到顺式和反式异构体的混合物，并且已将其分离出来。配合物反式-[FeI 2（depe）2 ]不溶于甲醇，但该配合物在该溶剂中的悬浮液与CO缓慢反应，生成顺式和反式-[Fe（CO）I（depe）2的混合物] +。反式-[FeX

  DOI：

  10.1039/dt9760001232
• 作为产物：
  描述：

  sodium iodide 、 (depe)₂FeCl₂ 以 甲苯 为溶剂， 反应 2.0h， 以98%的产率得到trans-Fe(depe)₂I₂
  参考文献：
  名称：

  Stepwise Construction of an Iron-Substituted Rigid-Rod Molecular Wire: Targeting a Tetraferra–Tetracosa–Decayne

  摘要：

  trans-Fe(depe)(2)I-2 (depe =1,2-bis(diethylphosphino)ethane) was employed to stepwise incorporate Fe(II) centers into a rigid-rod butadiyne based 5,10,15,20-tetraferratetracosa-1,3,6,8,11,13,16,18,21,23-decayne. The iterative synthesis first connects two Fe(II) centers via a central butadiynediyl ligand to provide I-Fe(depe)(2)-C-4-Fe(depe)(2)-I (2), then extends the system by substituting the terminal halides of 2 to yield Me3SiC4-Fe(depe)(2)-C-4-Fe(depe)(2)-C4SiMe3 (3). Further modification of the termini gives the deprotected and stannylated compounds RC4-Fe(depe)(2)-C-4-Fe(depe)(2)-C4R (4 and 5; R = H, Sn(CH3)(3), respectively). Transmetalation with two more mononuclear units furnishes the homometallic tetranuclear compound I-Fe(depe)(2)-C-4-Fe(depe)(2)-C-4-Fe(depe)(2)-C-4-Fe(depe)(2)-I (6), to which two more butadiynyl units were attached to give Me3SiC4-Fe(depe)(2)-C-4-Fe(depe)(2)-C-4-Fe(depe)(2)-C-4-Fe(depe)(2)-C4SiMe3 (7). All compounds were characterized by NMR, IR, and Raman spectroscopies and by elemental analyses. X-ray diffraction studies were carried out on the dinuclear complexes revealing highly symmetrical rigid-rod structures. Cyclic voltammetric studies showed that compounds 2-7 undergo reversible and well-defined oxidations with high K-c values indicating thermodynamically stable mixed valence species. While the number of the oxidation waves of compounds 2, 6, and 7 are equivalent to the number of metal centers, the dinuclear complexes 3, 4, and 5 exhibit three reversible oxidation waves, one at significantly more positive potential. Two redox waves were attributed to the oxidation of the metal centers, while the remaining one is due to the oxidation of the butadiynediyl ligand. The electronic properties of complexes 2, 3, and 7 were investigated by spectroelectrochemical measurements.

  DOI：

  10.1021/ja400078c

文献信息

• Structural and Electronic Variations of sp/sp² Carbon-Based Bridges in Di- and Trinuclear Redox-Active Iron Complexes Bearing Fe(diphosphine)₂X (X = I, NCS) Moieties
  作者：Franziska Lissel、Olivier Blacque、Koushik Venkatesan、Heinz Berke

  DOI：10.1021/om500602m

  日期：2015.1.26

  Starting from the mononuclear precursor trans-Fe(depe)2I2 (depe = 1,2-bis(diethylphosphino)ethane), four dinuclear complexes IFe(depe)(2)-R-Fe(depe)(2)I, with R = 1,4-(-C C-C6H4-C C-) 1, 1,3-(-C C-C6H4-C C-) 2, 4,4'-(-C C-C6H4-C6H4-C C-) 3, and 2,5-(-C C-thiophene-C C-) 4, as well as a trinuclear complex, I-Fe(depe)(2)(C C-)}3(1,3,5-C6H3)} 5, were prepared in a facile way by transmetalation from stannylated precursors. Substitution of the terminal iodides applying an excess of NaSCN yielded the corresponding isothiocyanate complexes 6-10 in very good yields. All complexes 1-10 are intrinsically functional due to the redox-active Fe centers embedded in a structurally rigid and covalent sp/sp(2) framework. 1-10 were characterized by NMR, IR, and Raman spectroscopy, as well as elemental analyses. X-ray diffraction studies were carried out for 1, 2, 4, 5, 6, 8, and 9. Cyclic voltammetry was employed to explore the redox behavior of 1-10. The 1,4-(-C C-C6H4-C C-) and the 2,5-(-C C-thiophene-C C-) bridged compounds 1, 4, 6, and 9 exhibit two fully reversible oxidation waves, while the 1,3-(-C C-C6H4-C C-) and 4,4'-(-C C-C6H4-C6H4-C C-) bridged dinuclear complexes and the trinuclear complexes show only one reversible oxidation wave corresponding to 2 e(-) and 3 e(-) processes, respectively. Calculations were carried out for truncated model complexes to determine the HOMO/LUMO energies. The DFT results confirmed that by changing the sp/sp(2) bridging ligand, tuning of the energies of the molecular orbitals and modifying of the HOMO-LUMO gap Delta E(H-L) and the chemical hardness are possible.