[Fe(η2-OCNiPr2)(CF3)(CO)2(PPh3)]

• 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: [Fe(η2-OCNiPr2)(CF3)(CO)2(PPh3)]
• 英文别名: Carbon monoxide;[di(propan-2-yl)amino]methanone;iron(2+);trifluoromethane;triphenylphosphane
• 化学式: C₂₈H₂₉F₃FeNO₃P
• 分子量: 571.359
• InChiKey: OZCLMWSFKHWDJJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.88
• 重原子数：
  37
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  22.3
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  [Fe(η2-OCNiPr2)(CF3)(CO)2(PPh3)] 在 NaC₅H₅*1,2-dimethoxyethane 作用下， 以 not given 为溶剂， 生成 tricarbonyl bis(triphenylphosphine) iron
  参考文献：
  名称：

  Carbamoyl (Carboxamido) Complexes as Precursors for Metallaoxetene, Isonitrile, and Aminomethylidyne Complexes of Iron

  摘要：

  The reaction of [Fe{C(=O)(NPr2)-Pr-i}(CO)(4)]Li with (CF3CO)(2)O in diethyl ether followed by triphenylphosphine provides carbamoyl complexes [Fe(eta(2)-(OCNPr2)-Pr-i}(CF3)(CO)(2)(PPh3)] (1) or [Fe(eta(2)-(OCNPr2)-Pr-i)(CO)(2)(PPh3)(2)](O2CCF3) (2a . O2CCF3) depending on the reaction conditions. The same procedure performed in dichloromethane provides the aminomethylidyne complex [Fe(=(CNPr2)-Pr-i)(CO)(3)(PPh3)](O2CCF3) (5 . O2CCF3) as well, as traces of [Fe(eta(2)-(OCNPr2)-Pr-i)(CO)(2)(PPh3)(2)](O2CCF3) (2a . O2CCF3). The reactions of 1 with moist AgBF4 or HBF4 provide [Fe(eta(2)-(OCNPr2)-Pr-i}(CO)(3)(PPh3)]BF4 (2b . BF4), via a putative difluorocarbene intermediate, [Fe(eta(2)-(OCNPr2)-Pr-i}(=CF2)(CO)(2)(PPh3)]BF4. In a similar manner, [Fe(eta(2)-(OCNPr2)-Pr-i)(CF3)(CO)(dppe)] (3) (obtained from 1 and dppe) reacts with HBF4(aq) to provide [Fe(eta(2)-(OCNPr2)-Pr-i}(CO)(2)(dppe)]BF4 (4 . BF4). A difluorocarbene complex is also implicated in the formation of the ferraoxetene [Fe{kappa(2)-C((NPr2)-Pr-i)OCF2}(CO)(HB(pz)(3)}] (6) (pz = pyrazol-1-yl), which results from treatment of 1 with K[HB(pz)(3)] under high dilution. Under more concentrated conditions [Fe(HB(pz)(3)}(2)] is obtained. The ferraoxetene undergoes an unusual acid hydrolysis with HBF4(aq)/CO to provide the isonitrile salt [Fe((CNPr)-Pr-i)(CO)(2){HB (pz)(3)}]PF6 (7 . PF6). The salt [Fe(=(CNPr2)-Pr-i)-(CO)(3)(PPh3)]I(5 . I) is the product of the reaction of 1 with iodine, via an as yet obscure mechanism, which may however also involve ferraoxetene intermediates.

  DOI：

  10.1021/om990385y
• 作为产物：
  描述：

  三氟乙酸酐 、 三苯基膦 、 lithium diisopropyl amide 、 iron pentacarbonyl 以 乙醚 为溶剂， 以56%的产率得到[Fe(η2-OCNiPr2)(CF3)(CO)2(PPh3)]
  参考文献：
  名称：

  Carbamoyl (Carboxamido) Complexes as Precursors for Metallaoxetene, Isonitrile, and Aminomethylidyne Complexes of Iron

  摘要：

  The reaction of [Fe{C(=O)(NPr2)-Pr-i}(CO)(4)]Li with (CF3CO)(2)O in diethyl ether followed by triphenylphosphine provides carbamoyl complexes [Fe(eta(2)-(OCNPr2)-Pr-i}(CF3)(CO)(2)(PPh3)] (1) or [Fe(eta(2)-(OCNPr2)-Pr-i)(CO)(2)(PPh3)(2)](O2CCF3) (2a . O2CCF3) depending on the reaction conditions. The same procedure performed in dichloromethane provides the aminomethylidyne complex [Fe(=(CNPr2)-Pr-i)(CO)(3)(PPh3)](O2CCF3) (5 . O2CCF3) as well, as traces of [Fe(eta(2)-(OCNPr2)-Pr-i)(CO)(2)(PPh3)(2)](O2CCF3) (2a . O2CCF3). The reactions of 1 with moist AgBF4 or HBF4 provide [Fe(eta(2)-(OCNPr2)-Pr-i}(CO)(3)(PPh3)]BF4 (2b . BF4), via a putative difluorocarbene intermediate, [Fe(eta(2)-(OCNPr2)-Pr-i}(=CF2)(CO)(2)(PPh3)]BF4. In a similar manner, [Fe(eta(2)-(OCNPr2)-Pr-i)(CF3)(CO)(dppe)] (3) (obtained from 1 and dppe) reacts with HBF4(aq) to provide [Fe(eta(2)-(OCNPr2)-Pr-i}(CO)(2)(dppe)]BF4 (4 . BF4). A difluorocarbene complex is also implicated in the formation of the ferraoxetene [Fe{kappa(2)-C((NPr2)-Pr-i)OCF2}(CO)(HB(pz)(3)}] (6) (pz = pyrazol-1-yl), which results from treatment of 1 with K[HB(pz)(3)] under high dilution. Under more concentrated conditions [Fe(HB(pz)(3)}(2)] is obtained. The ferraoxetene undergoes an unusual acid hydrolysis with HBF4(aq)/CO to provide the isonitrile salt [Fe((CNPr)-Pr-i)(CO)(2){HB (pz)(3)}]PF6 (7 . PF6). The salt [Fe(=(CNPr2)-Pr-i)-(CO)(3)(PPh3)]I(5 . I) is the product of the reaction of 1 with iodine, via an as yet obscure mechanism, which may however also involve ferraoxetene intermediates.

  DOI：

  10.1021/om990385y

文献信息

• Carbamoyl (Carboxamido) Complexes as Precursors for Metallaoxetene, Isonitrile, and Aminomethylidyne Complexes of Iron
  作者：Stephen Anderson、Anthony F. Hill、Ying Thong Ng

  DOI：10.1021/om990385y

  日期：2000.1.1

  The reaction of [FeC(=O)(NPr2)-Pr-i}(CO)(4)]Li with (CF3CO)(2)O in diethyl ether followed by triphenylphosphine provides carbamoyl complexes [Fe(eta(2)-(OCNPr2)-Pr-i}(CF3)(CO)(2)(PPh3)] (1) or [Fe(eta(2)-(OCNPr2)-Pr-i)(CO)(2)(PPh3)(2)](O2CCF3) (2a . O2CCF3) depending on the reaction conditions. The same procedure performed in dichloromethane provides the aminomethylidyne complex [Fe(=(CNPr2)-Pr-i)(CO)(3)(PPh3)](O2CCF3) (5 . O2CCF3) as well, as traces of [Fe(eta(2)-(OCNPr2)-Pr-i)(CO)(2)(PPh3)(2)](O2CCF3) (2a . O2CCF3). The reactions of 1 with moist AgBF4 or HBF4 provide [Fe(eta(2)-(OCNPr2)-Pr-i}(CO)(3)(PPh3)]BF4 (2b . BF4), via a putative difluorocarbene intermediate, [Fe(eta(2)-(OCNPr2)-Pr-i}(=CF2)(CO)(2)(PPh3)]BF4. In a similar manner, [Fe(eta(2)-(OCNPr2)-Pr-i)(CF3)(CO)(dppe)] (3) (obtained from 1 and dppe) reacts with HBF4(aq) to provide [Fe(eta(2)-(OCNPr2)-Pr-i}(CO)(2)(dppe)]BF4 (4 . BF4). A difluorocarbene complex is also implicated in the formation of the ferraoxetene [Fekappa(2)-C((NPr2)-Pr-i)OCF2}(CO)(HB(pz)(3)}] (6) (pz = pyrazol-1-yl), which results from treatment of 1 with K[HB(pz)(3)] under high dilution. Under more concentrated conditions [Fe(HB(pz)(3)}(2)] is obtained. The ferraoxetene undergoes an unusual acid hydrolysis with HBF4(aq)/CO to provide the isonitrile salt [Fe((CNPr)-Pr-i)(CO)(2)HB (pz)(3)}]PF6 (7 . PF6). The salt [Fe(=(CNPr2)-Pr-i)-(CO)(3)(PPh3)]I(5 . I) is the product of the reaction of 1 with iodine, via an as yet obscure mechanism, which may however also involve ferraoxetene intermediates.