| 169780-57-8

• CAS: 169780-57-8
• 化学式: C₁₄H₂₇FeN₂O₂PSi
• 分子量: 370.287
• InChiKey: HKLBXYMYTWCFAW-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：

  在 2BF₃*(C₂H₅)2O 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  阳离子过渡金属鏻配合物的反应性

  摘要：

  摘要 研究了阳离子过渡金属鏻配合物的反应性。mer-[(bpy)(CO)3M{PN(Me)CH2CH2NMe}]+ (M = Cr, Mo, W) 与 X−(X = Me, OEt) 的反应表现出对鏻磷的亲核攻击，而与 L (L = 膦，亚磷酸盐) 显示 CO/L 取代。铁鏻配合物 [Cp(CO)RFe-{PN(Me)CH2CH2NMe}]+ 经历鏻配体迁移插入 Fe-烷基键。

  DOI：

  10.1080/10426509608545107
• 作为产物：
  描述：

  [dicarbonyl(η5-cyclopentadienyl)iron]trimethylsilane 、 2-methoxy-1,3-dimethyl-1,3,2-diazaphospholane 以 苯 为溶剂， 以89%的产率得到
  参考文献：
  名称：

  磷配体向过渡金属烷基键的迁移插入

  摘要：

  Treatment of Cp(CO)(R(1))Fe{PN(Me)CH(2)CH(2)NMe(OR(2))} (R(1) = R(2) = Me, 1a; R(1) = Me, R(2) = Et, 2a; R(1) = CH(2)Ph; R(2) = Me, 3a) with BF3 . OEt(2) and then with PPh(3) yields [Cp(CO)(PPh(3))Fe{PN(Me)CH(2)CH(2)NMe(R(1))}](+) (R(1) = Me, 1b; R(1) = CH(2)Ph 3b). The reaction proceeds via the formation of a cationic phosphenium complex, [Cp(CO)(R(1))Fe{PN(Me)CH(2)CH(2)NMe}](+) by the abstraction of an OR group as an anion from a phosphorus atom, and then migratory insertion of the phosphenium ligand into the iron-alkyl bond takes place to give [Cp(CO)-(BF(2)OR(2))Fe{PN(Me)CH(2)CH(2)NMe(R(1))}](+), which is characterized by spectroscopic data. The cationic complex readily reacts with PPh(3) to give the final product. A eta(5)-C(5)Me(5) derivative of 1a and a monoamino-substituted phosphite complex Cp(CO)(Me)Fe{PN(Me)CH2CH2O-(OMe)} show the same reactivity. The reaction of silyl complexes Cp(CO)(SiMe(3))Fe-{PN(Me)CH(2)CH(2)NMe(OR)} (R = Me, Et) with BE(3) . OEt(2) affords a phosphenium complex [Cp(CO)(SiMe(3))Fe{PN(Me)CH(2)CH(2)NMe}](+), which does not show the migratory insertion into an iron-silyl bond. Iron complexes Cp(CO)(CH(2)OMe)Fe{PN(Me)CH(2)CH(2)NMe(OR)} (R = Me, 9a; R = Et, 10a) having an alkoxy group both on a carbon and on a phosphorus react with BF3 . OEt(2) and then with PPh(3) to give [Cp(CO)(CH(2)PPh(3))Fe{PN(Me)CH(2)CH(2)NMe(OR)}](+) (R = Me, 9e; R = Et, 10e). The results prove that the OME in the CH(2)OMe ligand is selectively abstracted to give the methylidene complex which is trapped with PPh(3) to give a phosphine ylide complex. Complexes 1b . BF4 and 10e . BF4 have been characterized by X-ray diffraction (crystal data for 1b . BF4, monoclinic, P2(1)/n, a = 9.099(1) Angstrom, b = 13.727 (2) Angstrom, c = 23.134 (5) Angstrom, beta = 91.48 (1)degrees, Z = 4, R = 0.063; for 10e . BF4, orthorhombic, Pcab, a = 18.033(6) Angstrom, b = 24.619 (6) Angstrom, c 14.501 (4) Angstrom, Z = 8, R = 0.059).

  DOI：

  10.1021/om00010a030

文献信息

• Comparison of the Reactivity of Cationic Phosphenium Complexes of Iron Containing a Group 14 Element Ligand
  作者：Hiroshi Nakazawa、Yoshitaka Yamaguchi、Kazumori Kawamura、Katsuhiko Miyoshi

  DOI：10.1021/om970480b

  日期：1997.10.1

  a Lewis acid (BF3·OEt2 or Me3SiOSO2CF3 (TMSOTf)) have been examined. The silyl complex 2a reacts with BF3·OEt2 to give a stable cationic phosphenium complex OMe anion abstraction from phosphorus. This reaction is in contrast to that of the corresponding alkyl complex reported earlier showing that the phosphenium complex once formed immediately undergoes migratory insertion of the phosphenium ligand

  已经研究了与路易斯酸（BF 3 ·OEt 2或Me 3 SiOSO 2 CF 3（TMSOTf））的反应= Si（2a），Ge（3a）和Sn（4a））。甲硅烷基络合物2a与BF 3 ·OEt 2反应，从磷中提取出稳定的阳离子Me络合物OMe阴离子。该反应与先前报道的相应烷基络合物的反应相反，后者表明一旦形成的complex络合物立即经历了mi配体向Fe-C键的迁移插入。X射线分析在Fe-P键中有相当大的双键特征。周围的Fe-P类（phOSphenium）键的旋转阻挡估计（Δ ģ ⧧（248 K）= 12.7千卡/摩尔）从一个变温1 1 H NMR研究。胚芽复合物3a具有与2a相同的反应性。相反，甲锡烷基络合物4a与TMSOTf反应以生成亚锡烷基（4e）。X射线分析表明，4e被认为是由OTf的氧-和一个氮的-氮稳定的双亚锡铁配合物。配体。在溶液中，在碱稳定的和无碱的亚锡形式之间存在平衡。中的激活参数（Δ
• C−C Bond Cleavage of Acetonitrile by a Carbonyl Iron Complex with a Silyl Ligand
  作者：Hiroshi Nakazawa、Takafumi Kawasaki、Katsuhiko Miyoshi、Cherumuttathu H. Suresh、Nobuaki Koga

  DOI：10.1021/om0208319

  日期：2004.1.1

  acetonitrile on the Fe coordination sphere with the activation energy of 15.0 kcal/mol take place to give Cp(CO)MeFe(CNSiMe3). The isolation of an iron complex with a methyl group derived from acetonitrile and a silylisocyanide ligand was attained in the photoreaction of Cp(CO)2Fe(SiPh3) in MeCN in the presence of PPh3. The product Cp (PPh3)MeFe(CNSiPh3) was confirmed by the X-ray structure analysis. The

  甲硅烷基铁配合物Cp（CO）2 Fe（SiMe 3）（1）在P（NMeCH 2）2（OMe）（L）存在下在乙腈中的光反应产生Cp（CO）LFeMe（2），CpL 2 FeMe（3）和CpL 2 Fe（CN）（4），表明实现了乙腈的碳-碳键裂解。这些C-C键裂解产物也是在L存在下，在THF中与1当量的MeCN在1中进行光反应而获得的。与CD 3 CN的反应表明，产物中铁的甲基衍生自乙腈。Cp（CO）的相应反应2 Fe（ER 3）（ER 3 = CH 3，GeMe 3，SnMe 3）生成了CO / L交换配合物Cp（CO）LFe（ER 3），表明铁上的甲硅烷基配体对于C是必不可少的乙腈的-C键裂解。使用杂化DFT-B3LYP方法进行了C-C键断裂的理论研究。乙腈对16e物种Cp（CO）Fe（SiMe 3）的直接C-C键氧化加成反应容易从1形成在光反应条件下，具有52.7kcal / mol的非