[FeCl2(bis(2-diphenylphosphinoethyl)methylamine)] | 435269-17-3

• 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: [FeCl2(bis(2-diphenylphosphinoethyl)methylamine)]
• 英文别名: dichloroiron;2-diphenylphosphanyl-N-(2-diphenylphosphanylethyl)-N-methylethanamine
• CAS: 435269-17-3
• 化学式: C₂₉H₃₁Cl₂FeNP₂
• 分子量: 582.272
• InChiKey: XMRGIKLBUJUORR-UHFFFAOYSA-L

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：

  [FeCl2(bis(2-diphenylphosphinoethyl)methylamine)] 以 乙醚 为溶剂， 以20%的产率得到
  参考文献：
  名称：

  Unrealized concepts of masked alkylidenes in (PNP)FeXY systems and alternative approaches to LnXmFe(IV)=CHR

  摘要：

  Treatment of PNP ligands with iron(II) halides yielded pseudo tetrahedral {(Ph2PCH2)(2)NR}FeX2 (R '' = Bu-t, 1a-X; Me, 1b-X) and {((Bu2PCH2)-Bu-i)(2)NR ''}FeX2 (R '' = Bu-t, 2a-X; Me, 2b-X) complexes, which could be mono- and dialkylated to afford various {(Ph2PCH2)(2)NR ''}FeCl(R) (R '' = Bu-t, 3a-R; Me, 3b-R), {((Bu2PCH2)-Bu-i)(2)NR ''}FeCl (R) (R '' = Bu-t, 4a-R; Me, 4b-R), {(Ph2PCH2)(2)(NBu)-Bu-t}Fe((neo)Pe)(2) (5a-(neo)Pe) and {((Bu2PCH2)-Bu-i)(2)(NBu)-Bu-t}Fe(1-nor)(2) (6a-nor). All of the complexes were high spin (S = 2), and structural studies of {(Ph2PCH2)(2)NMe}FeCl2 (1b-Cl), {((Bu2PCH2)-Bu-i)(2)(NBu)-Bu-t}FeCl2 (2a-Cl), and {((Bu2PCH2)-Bu-i)(2)(NBu)-Bu-t}FeCl(1-nor) (4a-nor), revealed chair conformations for the PNP ligands, which were calculated to have modest barriers to boat configurations via twist-boats as calculational minima. Attempts to convert these complexes to zwitterionic NCRR'Fe-containing species as "masked alkylidenes" failed to materialize. Alternative approaches involving structurally characterized diamagnetic {((Bu2PCH2)-Bu-i)(2)(NBu)-Bu-t}(CO)(2)FeCl(CO(neo)Pe) (8), the carbonylation product of 4a-neoPe, and low-valent {(Ph2PCH2CH2)(2)(NBu)-Bu-t}Fe((H2C=CHSiMe2)(2)O) (9) also failed. An analysis of orbital energies and overlap is given for alkylidenes. Covalence is identified as a crucial feature necessary for the alkylidene to metalacyclobutane transformation in metathesis. (C) 2020 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2020.114460
• 作为产物：
  描述：

  bis[(diphenylphosphanyl)ethyl]methylamine 、 iron(II) chloride 以 乙醚 为溶剂， 以61%的产率得到[FeCl2(bis(2-diphenylphosphinoethyl)methylamine)]
  参考文献：
  名称：

  Unrealized concepts of masked alkylidenes in (PNP)FeXY systems and alternative approaches to LnXmFe(IV)=CHR

  摘要：

  Treatment of PNP ligands with iron(II) halides yielded pseudo tetrahedral {(Ph2PCH2)(2)NR}FeX2 (R '' = Bu-t, 1a-X; Me, 1b-X) and {((Bu2PCH2)-Bu-i)(2)NR ''}FeX2 (R '' = Bu-t, 2a-X; Me, 2b-X) complexes, which could be mono- and dialkylated to afford various {(Ph2PCH2)(2)NR ''}FeCl(R) (R '' = Bu-t, 3a-R; Me, 3b-R), {((Bu2PCH2)-Bu-i)(2)NR ''}FeCl (R) (R '' = Bu-t, 4a-R; Me, 4b-R), {(Ph2PCH2)(2)(NBu)-Bu-t}Fe((neo)Pe)(2) (5a-(neo)Pe) and {((Bu2PCH2)-Bu-i)(2)(NBu)-Bu-t}Fe(1-nor)(2) (6a-nor). All of the complexes were high spin (S = 2), and structural studies of {(Ph2PCH2)(2)NMe}FeCl2 (1b-Cl), {((Bu2PCH2)-Bu-i)(2)(NBu)-Bu-t}FeCl2 (2a-Cl), and {((Bu2PCH2)-Bu-i)(2)(NBu)-Bu-t}FeCl(1-nor) (4a-nor), revealed chair conformations for the PNP ligands, which were calculated to have modest barriers to boat configurations via twist-boats as calculational minima. Attempts to convert these complexes to zwitterionic NCRR'Fe-containing species as "masked alkylidenes" failed to materialize. Alternative approaches involving structurally characterized diamagnetic {((Bu2PCH2)-Bu-i)(2)(NBu)-Bu-t}(CO)(2)FeCl(CO(neo)Pe) (8), the carbonylation product of 4a-neoPe, and low-valent {(Ph2PCH2CH2)(2)(NBu)-Bu-t}Fe((H2C=CHSiMe2)(2)O) (9) also failed. An analysis of orbital energies and overlap is given for alkylidenes. Covalence is identified as a crucial feature necessary for the alkylidene to metalacyclobutane transformation in metathesis. (C) 2020 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2020.114460

文献信息

• Synthesis of cobalt(II) and iron(II) complexes with the ligand bis(2-diphenylphosphinoethyl)methylamine and their catalytic action on ethylene oligomerization. X-ray crystal structure of [CoCl2{CH3N(CH2CH2PPh2)2}]
  作者：Mei Wang、Xiaomin Yu、Zhan Shi、Mingxing Qian、Kun Jin、Jiesheng Chen、Ren He

  DOI：10.1016/s0022-328x(01)01341-9

  日期：2002.2

  Complexes [MCl2CH3N(CH2CH2PPh2)2}] (1, M=Co; 2, Fe) were prepared by a modified procedure. The X-ray structural determination of 1 reveals that the cobalt(II) complex is four-coordinate with a distorted tetrahedral coordination geometry. The tertiary amine CH3N(CH2CH2PPh2)2 acts as a bidentate ligand through two phosphorus atoms. The CoP distances of 2.3666(14) and 2.3731(15) Å found in 1 are significantly

  配合物[MCl 2 CH 3 N（CH 2 CH 2 PPh 2）2 }]（1，M ＝ Co；2，Fe）通过改进的方法制备。X射线结构确定为1揭示钴（II）配合物为四坐标，且四面体配位几何形状失真。叔胺CH 3 N（CH 2 CH 2 PPh 2）2通过两个磷原子充当二齿配体。的2.3666（14）和2.3731（15）所涉及的CoP距离中发现的1比一般的CoP键长度长得多。在顶位置配体所处的不协调N原子反式到氯化物中的一个。研究了1和2与乙基铝氧烷（EAO）作为乙烯低聚助催化剂的催化性能。的活动89.4公斤低聚物摩尔-1 CO 2 H -1为1和81.2公斤低聚物摩尔-1的Feħ -1为2（100当量EAO的，180℃和1.8兆帕乙烯）以高选择性来直链C中观察到4-10个烯烃。